Novel substituted 1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamides and compositions and method for inhibiting pollen formation in corn

ABSTRACT

Novel compounds, e.g., 5,7-dimethyl-N-(2,6-dichlorolphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide and their compositions and use in the control of weeds and in the suppression of nitrification of ammonium nitrogen in soil. Other novel compounds and their compositions and use in the inhibition of bolting in sugar beets. Other novel compounds and their compositions and use as plant gametocides.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 768,393, filed Aug. 22,1985 abandoned and a continuation-in-part of application Ser. No.551,758 filed Nov. 14, 1983 also abandoned.

BACKGROUND OF THE INVENTION

In recent years there has been a great deal of effort directed to thedevelopment of sulfonamides having herbicidal activity and several ofthese compounds have reached the stage of commercialization, i.e.,chlorosulfuron and sulfometuron methyl. These compounds exhibit bothpreemergence and postemergence activity against undesirable vegetationand, in addition, have a low toxicity to mammals. The compounds of theprior art may be depicted as follows: ##STR1## wherein Ar is usually abenzene derivative and Ar' is usually a pyrimidine or symmetricaltriazine derivative.

In addition, there are a number of other sulfonamide herbicides thathave been commercialized, for example, methyl sulfanilylcarbamate;O,O-diisopropyl phosphorodithioate-S-ester withN-(2-mercaptoethyl)benzenesulfonamide;3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide;N-[2,4-dimethyl-5-[[(trifluoromethyl)sulfonyl]amino]phenyl]acetamide and3,5-dinitro-N⁴,N⁴ -dipropylsulfanilamide.

SUMMARY OF THE INVENTION

We have now found that compounds having the formula: ##STR2## wherein Arrepresents an aromatic (substituted or unsubstituted) or heteroaromatic(substituted or unsubstituted) ring system wherein the substituents areelectron withdrawing function groups in combination with other organicfunctional groups are exceptionally active herbicides and are active inthe suppression of nitrification of ammonium nitrogen in soil and areeffective in beneficially regulating the growth of crops and are readilyproduced. The aromatic ring may be monocyclic containing six carbonatoms or bicyclic containing ten carbon atoms. The heteroaromatic ringmay be monocyclic containing five or six atoms or bicyclic containingnine or ten atoms. The heteroatoms present in the heteroaromatic ringmay be one combination of one or more atoms such as nitrogen, oxygen orsulfur.

In addition certain derivatives of compounds of general formula (I) alsoexhibit herbicidal activity and suppression of nitrification of ammoniumnitrogen in soil and are effective in beneficially regulating the growthof crops and have the general formulas: ##STR3## wherein Ar representsan aromatic (substituted or unsubstituted) or heteroaromatic(substituted or unsubstituted) ring system.

DETAILED DESCRIPTION OF THE INVENTION

The aromatic or heteroaromatic ring systems include, for example,phenyl; 1- or 2-napthyl; 2-, 3- or 4-pyridyl; 2- or 3-thienyl; 2- or3-furyl; 2-, 4- or 5-thiazolyl; 2-, 4- or 5-imidazolyl; 2-, 4- or5-oxazolyl; 3-, 4- or 5-isothiazolyl; 3-, 4- or 5-isoxazolyl; 3-, 4- or5-pyrazolyl; 2-benzthiazolyl; 2-benzoxazolyl; 2-benzimidiazolyl and1-benztriazolyl. Typical examples of substituents found on the aromaticor heteroaromatic ring systems may be one, more than one or acombination of the following: halo (F, Cl, Br, I), C₁ -C₄ alkyl, C₁ -C₂mono-, di-, tri-, tetra- or perhaloalkyl, phenyl, hydroxy, alkoxy,haloalkoxy, phenoxy, substituted phenoxy, heteroaryloxy, substitutedheteroaryloxy, amino, alkylamino, dialkylamino, nitro, alkylthio,haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,haloalkylsulfonyl, substituted or unsubstituted phenylthio, substitutedor unsubstituted phenylsulfinyl, substituted or unsubstitutedphenylsulfonyl, cyano, carboxylic acids (and derivatives of carboxylicacids such as esters derived from readily available alcohols and amidesderived from ammonia or readily available primary and secondary amines),sulfonic acids (and derivatives of sulfonic acids such as sulfonatesderived from readily available alcohols and sulfonamides derived fromammonia or readily available primary or secondary amines), formyl,alkylcarbonyl, haloalkylcarbonyl, phenylcarbonyl, substitutedphenylcarbonyl, oximino, oxime ethers, carbinols (and carbinolderivatives such as ethers and esters derived from readily availablealkylating agents and carboxylic acids respectively) and mercaptoalkyl(and derivatives of mercaptoalkyl groups such as thioethers andthioesters derived from readily available alkylating agents andcarboxylic acids respectively).

The substituents on the triazolopyrimidine fragment of structure I arerepresented by X, Y and Z. Substituents X, Y and Z may be H, alkyl,haloalkyl, hydroxy, alkoxy, haloalkoxy, phenyl, substituted phenyl, halo(F, Cl, Br, I), alkylthio, phenylthio, amino (including alkyl or arylsubstituted amino), carboxylic acids and esters. In addition, twoadjacent substituents (i.e., X and Y or Y and Z) may be bonded togetherin a saturated five, six or seven-membered cyclic structure. Examples ofsuch cyclic structures could be represented by X and Y or Y and Z equalto --(CH₂)_(n) -- where n=3, 4 or 5. These cyclic structures may alsocontain heteroatoms (e.g. N, O or S) as in the case where X and Y or Yand Z is equal to --(CH₂)_(n) O-- where n=2 or 3. In the abovesubstitutents alkyl, alkenyl, alkynyl and alkoxy in each instance havefrom 1 to 10 carbon atoms.

Preferred compounds of the invention have the general formula: ##STR4##wherein R¹ represents halo (F, Cl, Br, I), --NO₂, phenyl, OAr, --CF₃,--OCF₃, --OCF₂ CF₂ H, --OCF₂ CCl₂ H, --OCH₂ CF₃, --SCF₃, --SCF₂ CF₂ H,--SCF₂ CCl₂ H, --SOCF₃, --SOCF₂ CF₂ H, --SOCF₂ CCl₂ H, --SO₂ CF₃, --SO₂CF₂ CF₂ H, --SO₂ CF₂ CCl₂ H, --SR⁶, --SOR⁶, --SO₂ R⁶, --CN, --COOR⁷,--CONH₂, --CONHR⁸, --CONR⁸ (R⁹), --SO₃ R⁸ and --SO₃ CH₂ CF₃ ; R² and R⁴represent H, halo (F, Cl, Br, I), C₁ -C₄ alkyl, COOR⁷ and --OR⁸ ; R³ isH; and R⁵ represents H, C₁ -C₄ alkyl, C₁ -C.sub. 4 alkoxy, halo (F, Cl,Br, I), NO₂, CF₃, --OCF₃, --OCF₂ CF₂ H, --OCF₂ CCl₂ H, --OCH₂ CF₃,--SCF₃, --SCF₂ CF₂ H, --SCF₂ CCl₂ H, --SOCF₃, --SOCF₂ CF₂ H, --SOCF₂CCl₂ H, --SO₂ CF₃, --SO₂ CF₂ CF₂ H, --SO₂ CF₂ CCl₂ H, --SR⁶, --SOR⁶,--SO₂ R⁶, --CN, --COOR⁷, --CONH₂, --CONHR⁸, --CONR⁸ (R⁹), --SO₃ R⁸,--SO₃ CH₂ CF₃, --CR⁶ R⁶ OR⁶ and --CR⁶ R⁶ SR⁶ wherein Ar representssubstituted or unsubstituted aryl or substituted or unsubstitutedheteroaryl, R⁶ represents H, aryl or C₁ -C₄ alkyl, R⁷ represents C₁ -C₆alkyl, alkenyl, alkynyl, aryl, substituted alkyl or substituted aryl andR⁸ and R⁹ individually represent C₁ -C₄ alkyl; and X, Y and Z representH, C₁ -C₄ alkyl, C₁ -C₄ alkoxy halo (F, Cl, Br, I), or X and Y or Y andZ can be joined to form a cycloalkyl ring (i.e., --(CH₂)_(n) -- whereinn is 3 or 4) or X and Y or Y and Z can be joined to form a ringcontaining a heteroatom (i.e., --O(CH₂)_(n) wherein n is 2 or 3).

Preferred compounds of the invention also have the general formula:##STR5## wherein R¹ represents H, alkyl or aryl, R² and R³ representindependently H, C₁ -C₄ alkyl, halo (F, Cl, Br, I), --NO₂, phenyl,--CF₃, benzyl, --COOR⁴, --CONH₂, --CONHR⁵, --CONR⁵ R⁶, and CN wherein R⁴represents C₁ -C₆ alkyl, alkenyl, alkynyl, arylalkyl, substituted alkylor substituted aryl, R⁵ and R⁶ individually represent C₁ -C₄ alkyl; andX, Y and Z represent H, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halo (F, Cl, Br,I), or X and Y or Y and Z can be joined to form a cycloalkyl ring (i.e.,--(CH₂)_(n) -- wherein n is 3 or 4) or X and Y or Y and Z can be joinedto form a ring containing a heteroatom (i.e., --O(CH₂)_(n) -- wherein nis 2 or 3.

Most preferred compounds of the invention have the general formula:##STR6## wherein R¹ represents C₁ -C₄ alkyl, halo (F, Cl, Br, I), --NO₂,--SR⁶, --SOR⁶, SO₂ R⁶, --COOR⁷ or CF₃ ; R² represents H, halo (F, Cl,Br, I), C₁ -C₄ alkyl, and COOR⁷ ; and R⁵ represents H, C₁ -C₄ alkyl, C₁-C₄ alkoxy, halo (F, Cl, Br, I), CH₂ OR⁶, phenyl, NO₂ and COOR⁷ whereinR⁶ represents C₁ -C₄ alkyl and R⁷ represents C₁ -C₄ alkyl, C₁ -C₄alkenyl, C₁ -C₄ alkynyl, 2-ethoxyethyl and 2-pyridylmethyl and X, Y andZ independently represent H, halo (F, Cl, Br, I), C₁ -C₄ alkyl or C₁ -C₄alkoxy.

Specifically preferred compounds of the invention include:

1.5,7-Dimethyl-N-)2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

2.5,7-Dimethyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

3.5,7-Dimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

4.5,7-Dimethyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

5.5,7-Dimethyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

6.5,7-Dimethyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

7.5,7-Dimethyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

8.5,7-Dimethyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

9.5,7-Dimethyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

10.5,7-Dimethyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

11.5,7-Dimethyl-N-(2-chloro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

12.5,7-Dimethyl-N-(2-fluoro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

13.5,7-Dimethyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

14.5,7-Dimethyl-N-(2-methyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

15.5,7-Dimethyl-N-(2-fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

16.5,7-Dimethyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

17.5,7-Dimethyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

18.5,7-Dimethyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

19.5,7-Dimethyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

20.5,7-Dimethyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

21.5,7-Dimethyl-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

22. Methyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

23. Ethyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

24. Isopropyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

25. 2-Ethoxyethyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

26. 2-Propen-1-yl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

27. 2-Pyridylmethyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

28. Methyl3-fluoro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

29. Ethyl3-fluoro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

30. Isopropyl3-fluoro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

31. Methyl3-chloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

32. Ethyl3-chloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

33. Isopropyl3-chloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

34. Methyl3-trifluoromethyl-n-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

35. Ethyl3-trifluoromethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

36. Isopropyl3-trifluoromethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

37. Methyl3,4-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

38. Ethyl3,4-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

39. Isopropyl3,4-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

40. Methyl3,6-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

41. Ethyl3,6-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

42. Isopropyl3,6-dimethyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

43. Methyl4-chloro-3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

44. Ethyl4-chloro-3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

45. Isopropyl4-chloro-3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

46. Methyl3-amino-2,4-dichloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

47. Ethyl3-amino-2,4-dichloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

48. Isopropyl3-amino-2,4-dichloro-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

49. Methyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

50. Ethyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

51. Isopropyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

52.5-Methyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

53.5-Methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

54.5-Methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

55.5-Methyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

56.5-Methyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

57.5-Methyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

58.5-Methyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

59.5-Methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

60.5-Methyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

61.5-Methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

62.5-Methyl-N-(2-chloro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

63.5-Methyl-N-(2-fluoro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

64.5-Methyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

65.5-Methyl-N-(2-methyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

66.5-Methyl-N-(2-fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

67.5-Methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

68.5-Methyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

69.5-Methyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

70.5-Methyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

71.5-Methyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

72.5-methyl-N-(2-acetyl-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

73.5-Methyl-N-(2,6-dichloro-3-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

74.5-Methyl-N-(2-methylthiomethyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

75.5-Methyl-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

76. Methyl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

77. Ethyl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

78. Isopropyl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

79. 2-Ethoxyethyl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

80. 2-Propen-1-yl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

81. 2-Pyridylmethyl3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

82. Methyl3-fluoro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

83. Ethyl3-fluoro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

84. Isopropyl3-fluoro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

85. Methyl3-chloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

86. Ethyl3-chloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2sulfonyl)anthranilate.

87. Isopropyl3-chloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

88. Methyl3-trifluoromethy-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

89. Ethyl3-trifluoromethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

90. Isopropyl3-trifluoromethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

91. Methyl3,4-dimethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

92. Ethyl3,4-dimethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

93. Isopropyl3,4-dimethyl-N-(5-methyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

94. Methyl3,6-dimethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

95. Ethyl3,6-dimethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

96. Isopropyl3,6-dimethyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

97. Methyl4-chloro-3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

98. Ethyl4-chloro-3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

99. Isopropyl4-chloro-3-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

100. Methyl3-amino-2,4-dichloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

101. Ethyl3-amino-2,4-dichloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

102. Isopropyl3-amino-2,4-dichloro-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

103. Methyl3-amino-2-bromo-4-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

104. Ethyl3-amino-2-bromo-4-methyl-N(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

105. Isopropyl3-amino-2-bromo-4-methyl-N-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

106.6-Methyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

107.6-Methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

108.6-Methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

109.6-Methyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-]pyrimidine-2-sulfonamide.

110.6-Methyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

111.6-Methyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

112.6-Methyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

113.6-Methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

114.6-Methyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

115.6-Methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

116.6-Methyl-N-(2-chloro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

117.6-Methyl-N-(2-fluoro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

118.6-Methyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

119.6-Methyl-N-(2-methyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

120.6-Methyl-N-(2-fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

121.6-Methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

122.6-Methyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

123.6-Methyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

124.6-Methyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

125.6-Methyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

126.6-Methyl-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

127. Methyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

128. Ethyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

129. Isopropyl3-methyl-N-(6-methyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

130. 2-Ethoxyethyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

131. 2-Propen-1-yl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

132. 2-Pyridylmethyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

133. Methyl3-fluoro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

134. Ethyl3-fluoro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

135. Isopropyl3-fluoro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

136. Methyl3-chloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

137. Ethyl3-chloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

138. Isopropyl3-chloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

139. Methyl3-trifluoromethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

140. Ethyl3-trifluoromethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

141. Isopropyl3-trifluoromethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

142. Methyl3,4-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

143. Ethyl3,4-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

144. Isopropyl3,4-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

145. Methyl3,6-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

146. Ethyl3,6-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

147. Isopropyl3,6-dimethyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

148. Methyl4-chloro-3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

149. Ethyl4-chloro-3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

150. Ispropyl4-chloro-3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

151. Methyl3-amino-2,4-dichloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

152. Ethyl3-amino-2,4-dichloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

153. Isopropyl3-amino-2,4-dichloro-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

154. Methyl3-amino-2-bromo-4-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

155. Ethyl3-amino-2-bromo-4-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

156. Isopropyl3-amino-2-bromo-4-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

157.7-Methyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

158.7-Methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

159.7-Methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

160.7-Methyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

161.7-Methyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

162.7-Methyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

163.7-Methyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

164.7-Methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

165.7-Methyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

166.7-Methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

167.7-Methyl-N-(2-chloro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

168.7-Methyl-N-(2-fluoro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

169.7-Methyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

170.7-Methyl-N-(2-methyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

171.7-Methyl-N-(2-fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

172.7-Methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

173.7-Methyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

174.7-Methyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

175.7-Methyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

176.7-Methyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

177.7-Methyl-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

178. Methyl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

179. Ethyl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

180. Isopropyl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

181. 2-Ethoxyethyl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

182. 2-Propen-1-yl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

183. 2-Pyridylmethyl3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

184. Methyl3-fluoro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

185. Ethyl3-fluoro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

186. Isopropyl3-fluoro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

187. Methyl3-chloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

188. Ethyl3-chloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

189. Isopropyl3-chloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

190. Methyl3-trifluoromethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

191. Ethyl3-trifluoromethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

192. Isopropyl3-trifluoromethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

193. Methyl3,4-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

194. Ethyl3,4-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.195. Isopropyl3,4-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

196. Methyl3,6-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

197. Ethyl 3,6-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

198. Isopropyl3,6-dimethyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

199. Methyl4-chloro-3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

200. Ethyl4-chloro-3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

201. Isopropyl4-chloro-3-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

202. Methyl3-amino-2,4-dichloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

203. Ethyl3-amino-2,4-dichloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

204. Isopropyl3-amino-2,4-dichloro-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

205. Methyl3-amino-2-bromo-4-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

206. Ethyl3-amino-2-bromo-4-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

207. Isopropyl3-amino-2-bromo-4-methyl-N-(7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

208.6-Chloro-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

209.6-Chloro-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

210.6-Chloro-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

211.6-Chloro-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

212.6-Chloro-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

213.6-Chloro-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

214.6-Chloro-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

215. Methyl3-methyl-N-(6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

216. Methyl3-fluoro-N-(6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

217.5-Methoxy-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

218.5-Methoxy-N-(2,methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

219.5-Methoxy-6-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

220.5-Methoxy-6-methyl-N-(2,5-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

221.5-Methoxy-6-methyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

222.5-Methoxy-6-methyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

223.5-Methoxy-6methyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

224.5-Methoxy-6-methyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

225.5-Methoxy-6-methyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

226.5-Methoxy-6-methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

227.5-Methoxy-6-methyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

228.5-Methoxy-6-methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

229.5-Methoxy-6-methyl-N-(2-chloro-6-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

230.5-Methoxy-6-methyl-N-(2-fluoro-6-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

231.5-Methoxy-6-methyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

232.5-Methoxy-6-methyl-N-(2-methyl-6-trifluoromethyl-phenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

233.5-Methoxy-6-methyl-N-(2-fluoro-6-trifluoromethyl-phenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

234.5-Methoxy-6-methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

235.5-Methoxy-6-methyl-N-(2,6-diflouro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

236.5-Methoxy-6-methyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

237.5-Methoxy-6-methyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

238.5-Methoxy-6-methyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

239. Methyl3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

240. Ethyl3-methyl-N-(5-methyoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

241. Isopropyl3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

242. 2-Ethoxyethyl3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

243. 2-Propen-1-yl3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

244. 2-Pyridylmethyl3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

245. Methyl3-fluoro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

246. Ethyl3-fluoro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

247. Isopropyl3-fluoro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

248. Methyl3-chloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

249. Ethyl3-chloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

250. Isopropyl3-chloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

251. Methyl3-trifluoromethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

252. Ethyl3-trifluoromethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

253. Isopropyl3-trifluoromethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

254. Methyl3,4-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

255. Ethyl3,4-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

256. Isopropyl3,4-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

257. Methyl3,6-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

258. Ethyl3,6-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

259. Isopropyl3,6-dimethyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

260. Methyl4-chloro-3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

261. Ethyl4-chloro-3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

262. Isopropyl4-chloro-3-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

263. Methyl3-amino-2,4-dichloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

264. Ethyl3-amino-2,4-dichloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

265. Isopropyl3-amino-2,4-dichloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

266. Methyl3-amino-2,4-dichloro-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

267. Ethyl3-amino-2-bromo-4-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

268. Isopropyl3-amino-2-bromo-4-methyl-N-(5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

269.5-Methyl-7-trifluoromethyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

270.5-Methyl-7-trifluoromethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

271.5-Methyl-7-trifluoromethyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

272.5-Methyl-7-trifluoromethyl-N-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

273.5-Methyl-7-trifluoromethyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

274.5-Methyl-7-trifluoromethyl-N-(2-chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

275.5-Methyl-7-trifluoromethyl-N-(2-fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

276.5-Methyl-7-trifluoromethyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

277.5-Methyl-7-trifluoromethyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

278.5-Methyl-7-trifluoromethyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

279.5-Methyl-7-trifluoromethyl-N-(2-chloro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

280.5-Methyl-7-trifluoromethyl-N-(2-fluoro-6-methoxymethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

281.5-Methyl-7-trifluoromethyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

282.5-Methyl-7-trifluoromethyl-N-(2-methyl-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

283.5-Methyl-7-trifluoromethyl-N-(2-fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

284.5-Methyl-7-trifluoromethyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

285.5-Methyl-7-trifluoromethyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

286.5-Methyl-7-trifluoromethyl-N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

287.5-Methyl-7-trifluoromethyl-N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

288.5-Methyl-7-trifluoromethyl-N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

289. Methyl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

290. Ethyl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

291. Isopropyl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

292. 2-Ethoxyethyl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

293. 2-Propen-1-yl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

294. 2-Pyridylmethyl3-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

295. Methyl3-fluoro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

296. Ethyl3-fluoro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

297. Isopropyl3-fluoro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

298. Methyl3-chloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

299. Ethyl3-chloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

300. Isopropyl3-chloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

301. Methyl3-trifluoromethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

302. Ethyl3-trifluoromethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

303. Isopropyl3-trifluoromethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

304. Methyl3,4-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

305. Ethyl3,4-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

306. Isopropyl3,4-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

307. Methyl3,6-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

308. Ethyl3,6-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

309. Isopropyl3,6-dimethyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

310. Methyl4-chloro-3-methyl-N-(5-methyl-y-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

311. Ethyl4-chloro-3-methyl-N-(5-methyl-y-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

312. Isopropyl4-chloro-3-methyl-N-(5-methyl-y-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

313. Methyl3-amino-2,4-dichloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

314. Ethyl3-amino-2,4-dichloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

315. Isopropyl3-amino-2,4-dichloro-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

316. Methyl3-amino-2,bromo-4-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

317. Ethyl3-amino-2,bromo-4-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

318. Isopropyl3-amino-2,bromo-4-methyl-N-(5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate.

319.N-(2-Trifluoromethylphenyl-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

320.N-(2,6-Dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

321.N-(2-6-Difluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

322.N-(2-Chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

323.N-(2-Bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

324.N-(2-Chloro-6-iodophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

325.N-(2-Fluoro-6-methylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

326.N-(2-Chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

327.N-(2-Bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

328.N-(2-Methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

329.N-(2-Chloro-6-methyloxymethylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

330.N-(2-Fluoro-6-methyloxymethylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

331.N-(2-Chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

332.N-(2-Methyl-6-trifluoromethylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

333.N-(2-Fluoro-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

334.N-(2,6-Dichloro-3-methylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

335.N-(2,6-Difluoro-3-methylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

336.N-(2,3-dimethyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

337.N-(3,6-dimethyl-2-nitrophenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

338.N-(2,3-dichloro-6-methylphenyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

339. Methyl3-methyl-N-(1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

340. Ethyl3-methyl-N-(1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

341. Isopropyl3-methyl-N-(1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

342. 2-Ethoxyethyl3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

343. 2-Propen-1-yl3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

344. 2-Pyridylmethyl3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

345. Methyl3-fluoro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

346. Ethyl3-fluoro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

347. Isopropyl3-fluoro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

348. Methyl3-chloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

349. Ethyl3-chloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

350. Isopropyl3-chloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)-anthranilate.

351. Methyl3-trifluoromethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

352. Ethyl3-trifluoromethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

353. Isopropyl3-trifluoromethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

354. Methyl3,4-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

355. Ethyl3,4-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

356. Isopropyl3,4-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

357. Methyl3,6-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

358. Ethyl3,6-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

359. Isopropyl3,6-dimethyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

360. Methyl4-chloro-3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

361. Ethyl4-chloro-3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

362. Isopropyl4-chloro-3-methyl-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

363. Methyl3-amino-2,4-dichloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

364. Ethyl3-amino-2,4-dichloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

365. Isopropyl3-amino-2,4-dichloro-N-(1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

366. Methyl3-amino-2-bromo-4-methyl-N-(1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)benzoate.

367. Ethyl3-amino-2-bromo-4-methyl-N-(1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)benzoate.

368. Isopropyl3-amino-2-bromo-4-methyl-N-(1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)benzoate.

369.5-Methyl-7-trifluoromethyl-N(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.

370.N(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

In addition, the following compounds are preferred due to their highlevels of herbicidal activity and selectivity to crop species:

1.5,7-Dimethyl-N-(2-chloro-1-napthyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

2.5-Methyl-N-(2-chloro-1-napthyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

3.5-Methyl-N-(1,3-dimethyl-5-trifluoromethyl-4-pyrazolyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

In addition, certain derivatives of compounds corresponding to I alsoexhibit herbicidal activity and nitrification inhibition activity insoil. For example, compounds having the formula: ##STR7## wherein Ar andX, Y and Z are as described above for compound I and R represents alkyl,alkenyl, alkynyl, phenylalkyl, substituted phenylalkyl, acyl,alkoxycarbonyl, phenoxycarbonyl, dialkylaminocarbonyl, alkylsulfonyl,phenylsulfonyl, alkylthiocarbonyl or phenylthiocarbonyl wherein alkyl,alkenyl and alkynyl are as above defined.

Preferred derivatives of the invention have the general formula:##STR8## wherein X, Y, Z, R¹, R², R³, R⁴ and R⁵ are as described abovefor I and R represents C₁ -C₄ alkyl, allyl, benzyl, --COR¹⁰, --CO₂ R¹⁰,--CONR₂ ¹⁰, --COSR¹⁰, and --SO₂ R¹⁰ wherein R¹⁰ is C₁ -C₆ alkyl, phenyl,substituted phenyl or C₁ -C₂ haloalkyl.

Most preferred derivatives of the invention have the general formula:##STR9## wherein X, Y, Z, R¹, R² and R⁵ are as described above for I andR is COR¹⁰ wherein R¹⁰ is C₁ -C₄ alkyl.

Specifically preferred derivatives of this embodiment of the inventioninclude all of the specifically preferred compounds listed previously inother embodiments of the invention wherein the hydrogen of thesulfonamide portion of their structures (SO₂ NH) has been replaced withany of the following groups:

1. COCH₃.

2. COCH₂ CH₃.

3. COCH₂ CH₂ CH₃.

4. COCH(CH₃)₂.

5. COCH₂ CH₂ CH₂ CH₃.

6. COCH₂ CH(CH₃)₂.

7. COCH₂ C(CH₃)₃.

8. COCH₂ C₆ H₅.

9. COcyclo--C₆ H₁₁.

10. COCH═CHC₆ H₅.

11. COC₆ H₅.

12. COCH₂ Cl.

13. COCH₂ CH₂ Cl.

14. COCH₂ CH₂ COOCH₃.

15. COCH₂ CH₂ COOCH₂ CH₃.

16. COOCH₃.

17. COOCH₂ CH₃.

18. CON(CH₃)₂.

19. C(O)SCH₃.

20. C(O)SCH₂ CH₃.

21. SO₂ CH₃.

22. SO₂ C₆ H₅.

Another series of derivatives of compounds of type I also possessherbicidal activity. These compounds are represented by the generalformula: ##STR10## wherein X, Y, Z and Ar are as described above forcompounds of type I.

Preferred derivatives of this invention have the general formula:##STR11## wherein X, Y, Z, R¹, R², R³, R⁴, and R⁵ are as described abovefor I.

Most preferred derivatives of this invention have the general formula:##STR12## wherein X, Y, Z, R¹, R² and R⁵ are as described above for I.

Specifically preferred derivatives of this invention include:

1.5,7-Dimethyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

2.5-Methyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

3.5,7-Dimethyl-N-(2-trifluoromethylphenyl)-4,5,6,7-tetrahydro-1,2,5-triazolo[1,5-a]pyrimidine-2-sulfonamide.

Furthermore, in the above invention corresponding to general formula IIIthe existence of stereoisomerism is possible. For example stereoiosmericrelationships exist when at least one of substituents X, Y and Z doesnot equal hydrogen. When only one of substituents X, Y and Z does notequal hydrogen the compound of type III may exist as a mixture ofenantiomers. One enantiomer will be designated as having theR-configuration and the other will be designated as having theS-configuration. Each enantiomer may exhibit different levels ofherbicidal activity. When two or more of substituents X, Y or Z instructure III do not equal hydrogen, the material may exist as a mixtureof diastereomers. For example when two substituents among X, Y and Z donot equal hydrogen, the compound may exist as two diastereomers. Whenall three of substituents X, Y and Z do not equal hydrogen the compoundmay exist as four diastereomers. In addition all of the diastereomersdescribed above exist as a mixture of two enantiomers. All of thestereoisomers described above, diastereomers and their enantiomericpairs, may exhibit different levels of herbicidal activity.

The synthesis of compounds of general structure I can be carried out ina straightforward manner as illustrated in Scheme I. Reaction ofsulfonyl chloride IV with the appropriate aromatic (substituted orunsubstituted) or heteroaromatic (substituted or unsubstituted) aminocompound (ArNH₂) under basic conditions yields the desired product I. Awide range of solvents may be employed (i.e., CH₂ Cl₂, CH₃ CN orpyridine) at temperatures ranging from 0° C. to reflux. Bases whichserve as catalysts include pyridine, 4-dimethylaminopyridine ad tertiaryalkylamines such as triethylamine or N-methylmorpholine. Generally theamino compound serves as the limiting reagent. Molar ratios of between1.1 and 1.0 for the sulfonylchloride to amino compound and molar ratiosof between 5.0 and 1.1 for the base to amino compound are used mostoften. A wide range of concentrations may be employed (i.e., 0.1-5M).Generally concentrations in the range of 0.5-2M are used to give ahomogeneous reaction which proceeds at a convenient rate. In addition itis sometimes advantageous to use a combination of pyridine derived basecatalysts and tertiary amine bases. The use of pyridine as a solvent isconvenient as the pyridine can serve both as a solvent and catalyst inthe transformation. ##STR13##

An additional alternative route to compounds of general formula I isillustrative in Scheme I. In cases where the amino compound (ArNH₂) isless reactive (less nucleophic) is it advantageous to prepare a metalderivative of the amino compound by treatment with a strong base. Thecorresponding amide bases are generally prepared in ether solvents(i.e., THF) using strong bases such as alkali metal alkyls (i.e.,n-BuLi) or alkali metal hydrides (i.e., NaH or KH) at temperaturesranging from -80° C. to 0° C. The amide thus generated in situ can bereacted with sulfonylchloride IV to yield the desired product I.Generally, molar ratios of the starting amino compound to sulfonylchloride of 2 to 3 are used to ensure complete reaction.

Sulfonyl chlorides IV are new and represent key intermediates in thesynthesis of sulfonamides I. Sulfonyl chlorides IV may be preparedaccording to routes outlined in Scheme II. Mercaptan IV may be convertedto sulfonyl chloride IV by treatment with Cl₂ in an aqueous acidicmedium. Generally the medium would be aqueous acetic acid or aqueousHCl. The temperature of the reaction mixture is generally maintainedbetween -20° C. and 25° C. during the course of the chlorine addition.Most preferably, temperature ranges between -20° C. and 0° C. areemployed to minimize unwanted side reactions such as hydrolysis of IV tothe corresponding sulfonic acid. Alternatively, the mercaptan IV may besuspended in a two phase system of aqueous acid (i.e., HCl) and anorganic solvent (i.e., CH₂ Cl₂) and treated with sodium hypochlorite.This serves to convert IV to the sulfonyl chloride IV in a reproduciblygood yield. The solubility of the product in the organic phase serves toprotect it from hydrolysis to the sulfonic acid. Again, temperatures inthe range of -20° C. to 25° C. are employed with temperatures in therange of -5° C. to 5° C. being most generally used. ##STR14##

As an alternative, it is sometimes preferred to prepare sulfonylchloride IV from benzyl sulfide VI (Scheme II). Reaction conditions asdescribed above for the conversion of V to IV are operable. Thisprocedure yields by-products containing benzyl residues which aregenerally removed by washing the product with water and/or anappropriate organic solvent and drying in vacuo.

Compounds of general structure V or VI may be prepared by routesillustrated in Scheme III. Some derivatives of structures V and VI areknown materials (i.e., V X═Z═Me, Y═H and VI X═Z═Me, Y═H) prepared bymethods described in J. Med. Chem., 25, 420 (1982). Compound IV isprepared directly by reaction of a 1,3-diketone with commerciallyavailable 3-amino-5-mercapto-1,2,4-triazole VII in glacial acetic acidas a solvent. Generally the reaction is performed at reflux.Alternatively, VII may be benzylated with benzyl chloride using analkali earth metal alkoxide (i.e., NaOH) as a base to yield known benzylsulfide VIII (J. Heterocycl. Chem., 12, 1187 (1975)). Benzyl sulfideVIII can be condensed with not only 1,3-diketones but also β-ketoesters, malonic esters, malonaldehyde, β-ketoaldehydes or α-formylesters or derivatives thereof (i.e., acetals or enol ethers) to yieldproducts of type VI as illustrated in Table A. Generally these reactionscan be carried out under acidic conditions (i.e., glacial acetic acid asa solvent) or basic conditions (i.e., NaOR in ROH wherein R is C₁ to C₄alkyl). In cases where the X, Y and Z substituents in VI are derivedfrom a 1,3-diketone, compound VI may be prepared by benzylation of IVusing an appropriate base (i.e., NaOH) and benzyl chloride in a varietyof solvents (i.e., H₂ O, CH₃ OH, EtOH, THF, dioxane, CH₃ CN, DMF or DMSOor combinations of the aforementioned). ##STR15##

                  TABLE A                                                         ______________________________________                                        1,3-Dicarbonyl          Compound of                                           Compound or   Reaction  Formula V or VI                                       Derivative    Conditions                                                                              X        Y    Z                                       ______________________________________                                                      acid      R        R'   R"                                       ##STR16##    acid      H        R'   R                                        ##STR17##    base      R        R'   H                                        ##STR18##    acid      OH*      R'   R                                        ##STR19##    acid      H        H    H                                        ##STR20##    base      OH       R'   OH                                      ______________________________________                                         *In this structural representation, as well as others bearing OH groups a     5 or 7positions of the 1,2,4triazolo[1,5-a]pyrimidine, the enol form has      been depicted. Clearly this is the equilibrium with the various keto          forms.                                                                   

In instances where the 1,3-dicarbonyl compound is unsymmetrical, thepossibility of obtaining two different isomers from condensation withVIII exists. In general, under acidic conditions the exocyclic nitrogenin VIII is the first to condense with the 1,3-dicarbonyl compound. Underbasic conditions the endocyclic nitrogen in VIII is sometimes morereactive. Consequently, in situations where a clear difference inreactivity of the two carbonyl functionalities in the 1,3-dicarbonylcompound exists, some measures of regiochemical control may be achievedby choice of reaction conditions (i.e., entries 2 and 3 in Table I).

To prepare the alternative regioisomer to that depicted in entry 4 inTable A (i.e., VI X═R, Y═R' and Z═OH) a route illustrated in Scheme IVwas followed. Compound VIII was condensed with 2,3-dibromocarboxylicacid esters to yield VI (X═R, Y═R', Z═OH). The reaction is generallycarried out in refluxing pyridine. ##STR21##

An additional route to compounds of type VI involves condensation ofcompound VIII with methanaminium compounds of type VII as illustrated inScheme V. The condensation is usually carried out by reaction inrefluxing glacial acetic acid and is useful in the synthesis of a numberof 6-substituted 1,2,4-triazolo[1,5-a]pyrimidines. ##STR22##

In the synthetic routes listed above, compounds of type VI where Xand/or Z is OH are capable of undergoing further transformation (SchemeVI). For example, treatment of compound VI (X and/or Z═OH) withphosphorus oxychloride yields VI (X and/or Z═Cl). The reaction isgenerally carried out at reflux in neat phosphorus oxychloride or withphosphorous oxychloride in a solvent (i e CH₃ CN). Compound VI (X and/orZ═Cl) can be further reacted with nucelophiles (i.e., NaOCH₃, MeMgBr) toyield VI (X and/or Z═OCH₃ or CH₃, respectively). In addition compound VI(X and/or Z═Cl) may be reduced to affort VI (X and/or Z═H). An effectivereducing agent for this type of transformation is zinc-copper couple inthe pressure of acid. ##STR23##

Other compounds of the present invention are best prepared in a mannerillustrated in Scheme VII. Compounds such as is represented by structureXI wherein X¹ and Z¹ are independently represented by hydrogen, C₁ -C₄alkyl, thioalkyl, thioaryl, amino (including mono- and disubstitutedalkylamino, mono- and disubstituted arylamino and arylalkylamino) can beprepared by this method. The method involves the reaction of compound Xwherein X and Z independently represents hydrogen, C₁ -C₄ alkyl or anappropriate leaving group, with a nucleophile in a suitable solvent.This procedure affects the substitution of the leaving group by thenucleophilic unit. A representative leaving group that is effective inthis process is trifluoroethoxide (⁻ OCH₂ CF₃). Representativenucleophiles for this process include alkali metal salts of alkylmercaptans, alkali metal salts of aryl mercaptans, ammonia, primary andsecondary alkylamines, primary and secondary arylamines, secondaryarylalkylamines, and alkali metal salts of hydroxides. Thesenucleophiles result in the displacement of the leaving group (X and/orZ) in compound V to produce compound XI containing X¹ and/or Z¹represented as alkylthio, arylthio, amino, mono- and disubstitutedalkylamino, mono- and disubstituted arylamino, arylalkylamino orhydroxyl respectively. Suitable solvents for this transformation includepolar aprotic solvents (i.c., DMSO, DMF), alcohols and water. Suitablereaction temperatures range from 0° C. to 100° C. although thetemperature of the reaction is usually not critical. Reactiontemperatures of 20° C. to 30° C. are most frequently employed. ##STR24##

In addition certain compounds of the present invention containg ahalogen in the 6-position on the 1,2,4-triazolo[1,5-a]pyrimidine ringsystem may be prepared by halogenation of the corresponding6-unsubstitued compound. This is illustrated in Scheme VIII. In generalN-halo-succinimide derivatives are the halogenating agents of choice.Reactions are often performed in acid solvents at temperatures rangingfrom room temperature to 150° C. ##STR25##

Another method to prepare the compounds of the present invention isillustrated in Scheme IX. Compounds of general structure I can beoxidized to yield compounds of structure XII. Oxidizing agents capableof this transformation include various transition metal oxidants such asderivatives of hexavalent chromium (Cr^(VI)) or heptavalent manganese(Mn^(VII)), organic peracids or peroxides. Oxidizing agents such aspotassium permanganate, chromium trioxide, peracetic acid and hydrogenperoxide are frequently employed. Preferred conditions for theconversion of I to XII involve reaction of I with two to five molarequivalents of potassium permanganate in 0.1N to 1.0N aqueous alkalimetal hydroxide (i.e., NaOH or KOH) as a solvent. The reaction may berun at temperatures ranging from ambient temperature to reflux. Mostcommonly the reaction is run at 50° C. to 60° C. The product of thisreaction (XII) can be hydrolyzed to compound XIII by treatment withaqueous acid in an organic co-solvent. Typical acids includehydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid ormethane sulfonic acid. Appropriate organic co-solvents include acetone,methyl ethyl ketone, ethanol, acetonitrile or tetrahydrofuran. Lastly,compound XIII can be reconverted to a compound of general structure I bycyclization with a 1,3-dicarbonyl compound or an equivalent of a1,3-dicarbonyl compound. The conditions for this cyclization, thestructural requirements for the 1,3 dicarbonyl compound or an equivalentand structural considerations for the product are as describedpreviously for the conversion of VII and V and VIII to VI. ##STR26##

The method for the preparation of compounds of structure I asillustrated in Scheme IX is employed advantageously in certainsituations. Various functional groups present on the1,2,4-triazolo-[1,5-a]pyrimidine ring system (X, Y and Z) of I whichimpart useful herbicidal, nitrification inhibitory or plant growthregulatory activity can only be produced in low yield by previouslydescribed routes. The primary cause for the low yield in the previouslydescribed routes is the incompatability of the function group or thering system which bears the functional group to the conditions requiredto form the required sulfonyl chlorides IV. Examples of substituents (X,Y and Z) present in compounds of structure I which are advantageouslyprepared by the method outlined in Scheme IX include H, halo (F, Cl, Brand I), hydroxy, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkysulfinyl, C₁ -C₄ alkylsulfonyl, C₁ -C₄ mono- or polyhaloalkyl, C₁-C₄ mono- or polyhaloakoxy, C₁ -C₄ mono- or polyhaloalkylthio, C₁ -C₄mono- or polyhaloalkylsulfinyl, C₁ -C₄ mono- or polyhaloalkylsulfonyl,amino, C₁ -C₄ mono- or dialkylamino, phenyl, substituted phenyl,phenoxy, substituted phenoxy, thiophenyl, phenylsulfinyl,phenylsulfonyl, substituted thiophenyl, substituted phenylsulfinyl,substituted phenylsulfonyl, carboxyl, and carboxyl derivatives such asesters derived from C₁ -C₄ alcohols. The substituents X and Y or Y and Zcan also be joined to form a ring containing a total of five to sevenatoms. This ring may contain heteroatoms (i.e., nitrogen, oxygen orsulfur), unsaturation (i.e., --CO-- or --C═C--) or a halogensubstituent.

The compounds of structure I which are most advantageously prepared bythe method outlined in Scheme IX contain substituents (X, Y and Z) whichare one or more of the following: H, halo (F, Cl, Br and I), C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄alkylsulfonyl, C₁ -C₄ mono- or polyhaloalkyl, C₁ -C₄ mono- orpolyhaloalkoxy, C₁ -C₄ mono- or polyhaloalkylthio, C₁ -C₄ mono- orpolyhaloalkylsulfinyl, C₁ -C₄ mono- or polyhaloalkylsulfonyl, amino andC₁ -C₄ mono- or dialkylamino.

Specifically preferred substituent patterns of structure I which may beprepared by the method outlined in Scheme IX are the following:

1. X═Y═Z═H

2. X═CF₃, Y═H and Z═CH₃

3. X═Z═CF₃ and Y═H

4. X═Cl, Y═H and Z═CH₃

5. X═OCH₃, Y═H and Z═CH₃

6. X═OCH₂ CF₃, Y═H and Z═CH₃

7. X═SCH₃, Y═H and Z═CH₃

8. X═N(CH₃)₂, Y═H and Z═CH₃

The starting material of structure I in the reaction sequence of SchemeIX may contain one or more of the following substituents: H, halo (F,Cl, Br and I) and C₁ -C₄ alkyl. The intermediates (XII and XIII) are newcompounds. The aromatic ring in the starting material I andintermediates XII and XIII is as described previously for structure I.The R group in intermediates XII may be H or CH₃.

Compounds of the present invention represented by structure II arederived from compounds represented by structure I as illustrated inScheme X. The derivatization procedure involves treatment of compound Iwith a base in a suitable solvent followed by the introduction of anappropriate electrophilic derivatizing reagent. From this processcompounds of general structure II can be isolated in good yields.Suitable bases include tertiary alkylamines (i.e., triethylamine),pyridine, 4-dimethylaminopyridine, alkali metal carbonate (i.e, Na₂ CO₃or K₂ CO₃) and alkali metal alkoxides (i.e, sodium ethoxide or potassiumt-butoxide). Suitable solvents include ethers (i.e., tetrahydrofuran),pyridine, acetone, acetonitrile, alcohols (i.e., methanol, ethanol,isopropanol and t-butanol) and polar aprotic solvents (i.e., DMSO andDMF). Suitable electrophilic reagents include alkyl halides, arylalkylhalides (i.e., benzyl chloride), carboxylic acid chlorides, alkyl chloroformates, aryl chloro formates, N,N-dialkyl carbamoyl chlorides, alkylsulfonyl chlorides, aryl sulfonyl chlorides, alkyl chloro thioformates##STR27## and aryl chlorothioformates ##STR28##

Compounds of the present invention represented by structure III are alsoderived from compounds represented by structure I as illustrated inScheme XI. The general process involves the reduction of compounds ofgeneral structure I with an appropriate reducing agent in a suitablesolvent to yield compounds of general structure III. Reducing agentswhich are effective include metal hydrides (i.e., sodium borohydride) inthe presence of acids (i.e., methane sulfonic acid) and hydrogen in thepresence of a normal hydrogenation catalyst (i.e., palladium on carbon).For reductions with metal hydrides polar aprotic solvents (i.e., DMSO)are most frequently used. For reductions using hydrogen and a catalystalcohols (i.e, ethanol) are most frequently employed as solvents.##STR29##

The majority of the amino compounds (ArNH₂) utilized to prepare thecompounds of the present invention (see structure I) as illustrated inScheme I were obtained from commercial sources or prepared by knownliterature procedures or minor modifications of literature procedures.

A number of the amino compounds (ArNH₂) used to prepare the compounds ofthe present invention are derivatives of anthranilic acid. Many of thesecompounds can be prepared according to conventional methods described byS. J. Holt et al., Royal Soc. Proc. Sec. B, 148, 481 (1958), P. W.Sadler et al., J. Am. Chem. Soc., 78, 1251 (1956), and G. Reissenweberet al., U.S. Pat. No. 4,310,677 (1982). Other anthranilic acidderivatives can be prepared by standard derivatizations (i.e.,conversion to esters and amides) of known substituted or unsubstituted2-nitrobenzoic acids followed by reduction of the nitro group asrepresented in Scheme XII. ##STR30##

A number of the amino compounds are prepared by reduction of anthranilicacids or esters and subsequent derivatization of the reduction product.This is outlined in Scheme XIII. The carbinol reduction products may bederivatized by reaction with base and various electrophiles (i.e., alkylhalides and carboxylic acid chlorides). ##STR31##

A large number of the amino compounds utilized in the preparation of thecompounds of this invention contain halogen substituents ortho to theamino group. Many of these compounds were prepared by halogenation ofthe corresponding material bearing no substituent in the ortho positionaccording to a general procedure described by R. S. Neale et al., J.Org. Chem., 29, 3390 (1964). The starting materials for thesehalogenations were commercially available or known in the literature(i.e., British Patent No. 695,164 (1953); D. S. Noyce et al., J. Org.Chem. 26, 1732 (1961) and U.S. Pat. No. 3,813,234 (1974)). In certaininstances to facilitate the transformation and insure ortho selectivityin the halogenation process the starting materials for the halogenationwere acetamide derivatives (ArNHCOCH₃) or derivatives containing groups(i.e., Br) which would block halogenation at other positions in themolecule (i.e., para to the amino group). Following halogenation theacetamide derivatives were hydrolized back to the desired amino compoundand the blocking groups were removed (i.e., Br in the para position wasselectively removed by reduction in the presence of --Cl in the orthoposition). Other chlorine and bromine substituted amino compounds wereprepared by known procedures (i.e., U.S. Pat. No. 4,188,342 (1980); C.R. Rasmussen et al. J. Med. Chem., 21, 1044 (1978); H. E. Dadswell etal. J. Chem. Soc., 1102 (1927); U.S. Pat. No. 3,813,234 (1974) and P. B.D. DeLaMare and J. H. Ridd, "Aromatic Substitution, Nitration andHalogenation", Academic Press, New York (1959), P. 106.

A number of the amino compounds used as starting materials for thecompounds of this invention contain sulfur substituents in the orthoposition. These were prepared using known procedures (i.e., R. R. Guptaet al Heterocycles, 16, 1527 (1981) and J. P. Chupp et. al., J. Org.Chem., 49, 4711 (1984)). In some cases alkylthio groups were present andthese were synthesized by alkylation of the corresponding mercaptan.Compounds having alkyl or aryl sulfinyl or sulfonyl groups weresynthesized by oxidation of the appropriate alkyl or arylthio groups.

Some starting amino compounds containing amino, alkylamino, aryloxy orpyridyloxy groups were prepared by catalytic reduction of thecorresponding nitro compounds. The amino, alkylamino, aryloxy orpyridyloxy group were usually introduced via displacement of a leavinggroup ortho to the nitro group in the requisite nitrobenzene.

Other starting amino compounds were prepared by procedures involvingmetalation of the aromatic ring of N-substituted derivatives (i.e.,t-butoxycarbonyl derivatives) of an aromatic amino compound followed bythe resulting organometallic reagent with an electrophile. This generalprocedure is described in H. Gschwend, Org. Reactions, Vol. 20, 1-360(1979) and is outlined in Scheme XIV. Suitable metalating agents areorganolithium reagents (i.e., n-butyllithium or t-butyllithium). Typicalelectrophiles include alkyl halides (i.e., methyl iodide, ethyl iodide),aldehydes (i.e., formaldehyde, acetaldehyde), ketones (i.e., acetone),alkyl or aryl sulfonyl halides (i.e., methyl sulfenyl chloride), anddialkyl or diaryldisulfides (i.e., dimethyldisulfide). Theseelectrophiles are useful for the introduction of alkyl, hydroxy alkyland arylthio or arylthio groups to the position ortho to the aminogroup. After the reaction of the organometallic intermediate with theelectrophile the nitrogen substituent is removed by hydrolysis.##STR32##

Other aromatic amino compounds used to prepare compounds of the presentinvention are prepared by conversion of carboxylic acid groups orderivatives of carboxylic acid groups to amino groups by standardmethodology. Such a transformation is illustrated in Scheme XV anddescribed in J. Royal. Netherlands Chem. Soc., 97, 53 (1978) ##STR33##

Other amino compounds such as those which are heteroaromatic aminocompounds are prepared by known procedures such as those described inRec. Trav. Chim., 69, 673 (1950), T. Talik et al., Chem. Abstracts, 59:869a (1963) and L. C. Behr and R. Fusco in "Heterocyclic Compounds", A.Weissberger, Ed. Vol 22, Interscience Publishers, New York (1967), p3-174 or straightforward modification of the art described above.

Other amino compounds used to prepare compounds of the present inventionare prepared by direct metalation of the aromatic ring. This isillustrated schematically in Scheme XVI. An aromatic ring bearing one tothree substituents on the ring may be metalated with an alkyl lithiumreagent (i.e. n-butyl lithium, s-butyl lithium or t-butyl lithium) toform an aryl lithium intermediate. This reaction is most frequentlycarried out in an etherial solvent (i.e. diethyl ether, tetrahydrofuranor 1,2-dimethoxyethane) at temperature ranging from -78° C. to ambienttemperature. It is sometimes advantageous to perform the metalationreaction in the presence of additives such astetramethylethylenediamine. The aryl lithium reagent is generated insitu and is reacted with carbon dioxide followed by protonation of theresultant carboxylate to form the carboxylic acid. The carboxylic acidcan then be converted to the corresponding amino compound by standardmethodology of the Hoffman, Curtius, Lossen and Schmidt reactions.##STR34##

The substituents (R¹, R², and R³), which are operable in the processillustrated in Scheme XVI are as follows: R¹, R², and R³ may be chosenfrom among H, halogen (F, Cl, Br and I), C₁ -C₄ alkyl, C₁ -C₄ mono- orpolyhaloalkyl or C₁ -C₄ alkoxy. Most preferred substituents are R¹ isequal to H or C₁ -C₄ alkyl; R² and R³ are equal to halo (F or Cl), C₁-C₄ mono- or polyhaloalkyl or C₁ -C₄ alkoxy.

The intermediate carboxylic acid formed as illustrated in Scheme XVI orderivatives of the carboxylic acid (i.e. esters and amides) can beutilized to prepare other amino compounds which are useful in thepreparation of compounds I of the present invention. This process isillustrated in Scheme XVII. When the carboxylic acid product contains aleaving group such as a halogen atom (i.e. F, Cl or Br) at an adjacentposition, the carboxylic acid may be converted to a suitable derivativeand the halogen may then be replaced by displacement with a suitablenucleophile. Nucleophiles which are useful in this case include ammonia,C₁ -C₄ monoalkyl amines, C₁ -C₄ dialkylamines, C₁ -C₄ alkali metalalkoxides, C₁ -C₄ alkali metal mono- or polyhaloxides or C₁ -C₄ alkalimetal mercaptides. The use of these nucleophiles serves to replace thehalogen substituent with amino, C₁ -C₄ monoalkylamino, C₁ -C₄dialkylamino, C₁ -C₄ alkoxy, C₁ -C₄ mono- or polyhaloalkoxy or C₁ -C₄alkylthio respectively. The resultant products of the nucleophilicdisplacement can be converted to the corresponding amino compound bystandard methodology of the Hoffman, Curtius, Lossen and Schmidtreactions. ##STR35## R² or R³ =halogen X=OH, OR⁴ N(R⁴)₂ where R⁴ =H orC₁ -C₄ alkyl.

Other amino compounds which are sueful in the preparation of compounds Iof the present invention can be prepared as illustrated in Scheme XVIII.The starting material for this procedure is 2,6-difluoroaniline. Theamino group of the aniline is protected with a silyl protecting groupaccording to a general procedure described by Magnus et. al inTetrahedron Lett., 1787 (1981) ad Guggenheim et. al. in TetrahedronLett., 1253 (1984). The protected aniline can then be metalated with analkyl lithium reagent (i.e. n-butyl lithium, s-butyl lithium or t-butyllithium) to form the corresponding aryl lithium reagent. The metalationis best carried out in etherial solvents such as diethyl ether,tetrahydrofuran or dimethoxyethane at temperatures ranging from -78° C.to ambient temperature. It is sometimes advantageous to carry out themetalation in the presence of additives such tetramethylethylenediamine.The aryl lithium reagent is formed in situ and can be reacted with avariety of electrophilic reagents such as C₁ -C₄ alkyl halides, C₁ -C₄dialkyldisulfides or C₁ -C₄ alkyl sulfenyl halides, dimethylformamide,C₁ -C₄ acyl halides or C₁ -C₄ N-methyl-O-methyl alkylhydroxamates, C₁-C₄ alkyl chloroformates and carbon dioxide. These electrophilicreagents serve to introduce C₁ -C₄ alkyl, C₁ -C₄ alkylthio, formyl, C₁-C₄ acyl, C₁ -C₄ alkoxycarbonyl and carboxyl groups respectivelydirectly into the 3-position of the aromatic ring. The product fromelectrophilic substitution can be protected using standard methodologyas described in the literature to form the desired amino compound.##STR36##

The table which follows contains a listing of aromatic amino compoundsprepared by methods described above and not previously described inknown art which are useful in the preparation of the biologically activecompounds of this invention.

    ______________________________________                                         ##STR37##                                                                    Com-                                                                          pound R.sup.1       R.sup.2   R.sup.3                                                                           R.sup.4                                                                           R.sup.5                                 ______________________________________                                        A   Cl              COOCH.sub.3                                                                             H   H   Cl                                      B   Br              COOCH.sub.3                                                                             H   H   CH.sub.3                                C   CH.sub.3        Cl        H   H   COOCH.sub.3                             D   Cl              CF.sub.3  H   H   Cl                                      E   Cl              Cl        Br  H   CH.sub.3                                F   Cl              Cl        H   H   CH.sub.3                                G   Cl              H         H   H   CH.sub.2 COH.sub.3                      H   Cl              H         H   H   CH.sub.2 OAC                            I   Cl              H         H   H   CH.sub.2 OCH.sub.2 Ph                        ##STR38##      H         H   H   H                                       K                                                                                  ##STR39##      H         H   H   H                                       L                                                                                  ##STR40##      H         H   H   F                                       M   F               H         H   H   SCH.sub.3                               N   CF.sub.3        H         H   H   OCH.sub.3                               O   CF.sub.3        H         H   H   N(CH.sub.3).sub.2                       ______________________________________                                    

Using the routes illustrated above or minor variations based on theprinciples illustrated above the novel compounds of this invention canbe prepared.

The invention is further illustrated by the following examples.

EXAMPLE 1 Preparation of5,7-dimethyl-2-mercapto-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 10.1 g (0.0870 mol) of 3-amino-5-mercapto-1,2,4 triazole,8.71 g (0.0870 mol) of 2,4-pentandione and 0.8 ml of piperidine in 300ml of HOAc was heated at reflux for 21.5 hours. After cooling to roomtemperature, the solid which separated was collected by filtration anddried in vacuo to yield 13.4 g of pale yellow needles, m.p. 245°-246° C.(decomposition); ¹ H NMR (DMSO-d₆ --CDCl₃) δ13.9 (1H, broad, SH), 7.19(1H, broad s, H in 6-position) 2.63 and 2.51 (3H each, s, CH₃ groups in5- and 7-positions), IR (KBr) ˜2680, 1628, 1560, 1400 and 1170 cm⁻¹. Ananalytical sample was prepared by recrystallization from acetic acid toyield colorless plates, m.p. 243.5°-244.5° C. (decomposition).

Analysis: Calculated for C₇ H₈ N₄ S: C, 46.65; H, 4.47; N, 31.09; Found:C, 46.34; H, 4.41; N, 30.82.

EXAMPLE 2 Preparation of2-benzylthio-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

Twenty percent NaOH (14.0 g, 70 mmol) was added dropwise to a suspensionof 11.5 g (64.0 mmol) of the mercaptan prepared in Example 4 in 125 mlof H₂ O over about 5 minutes. Benzyl chloride (7.4 ml, 8.1 g, 64 mmol)in 20 ml of CH₃ OH was added and the resulting mixture was vigoruslystirred at room temperature for 24 hours. The solid which beganseparating shortly after the addition of benzyl chloride was collectedby filtration and dried in vacuo to afford 16.1 g of white solid, m.p.134°-135° C. (lit m.p. 132°-134° C., T. Novinson et al, J. Med. Chem.,25, 420 (1982)): ¹ H NMR (CDCl₃) δ7.1-7.6 (5H, m. Ph), 6.63 (1H, s, H in6-position), 4.50 (2H, s, --CH₂ S--), 2.67 and 2.58 (3H each, s, CH₃groups in 5- and 7-positions); IR (CHCl₃) 1620, 1447, 1339 and 1295cm⁻¹. 93% yield.

Analysis: Calculated for C₁₄ H₁₄ N₄ S: C, 62.20; H, 5.22; N, 20.72;Found: C, 62.21; H, 5.14; N, 20.89.

EXAMPLE 3 Preparation of2-benzylthio-6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 51.6 g (0.250 mol) of 3-amino-5-benzylthio-1,2,4-triazoleand 31.5 g (0.250 mol) of 2-acetylcyclopentanone in 600 ml of HOAC washeated at reflux for 9.5 hours. The solvent was removed by evaporation,and the brown solid residue was recrystallized from EtOH to yield alight brown solid. A second recrystallization from EtOH gave 45.4 g (61percent) of the desired product as a light brown solid, m.p. 157°-158.5°C.: ¹ H NMR (CDCl₃) δ7.0-7.6 (5H, m), 4.51 (2H, s), 3.29 (2H, t), 2.97(2H, t), 2.0-2.7 (5H, m including s at 2.52); IR (CHCl₃) 1621, 1343 and1290 cm⁻¹.

Analysis: Calculated for C₁₆ H₁₆ N₄ S: C, 64.84; H, 5.44, N, 18.90; S,10.82. Found: C, 64.88; H, 5.47; N, 18.98; S, 10.72.

EXAMPLE 4 Preparation of2-benzylthio-5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 51.6 g (0.250 mol) of 3-amino-5-benzylthio-1,2,4-triazoleand 28.5 g (0.250 mol) of 3-methyl-2,4-pentanedione in 350 ml of glacialacetic acid was heated at reflux for 17 hours. Upon cooling to roomtemperature, the reaction mixture was poured onto ice. The pale yellowsolid which separated was collected by filtration, washed with water anddried in vacuo to yield 67.1 g (94%) of the desired product as a paleyellow solid, m.p. 133.5°-135° C. The IR and ¹ H NMR spectra wereconsistent with the assigned structure.

Analysis: Calculated for C₁₅ H₁₅ N₄ S: C, 63.35; H, 5.67; N, 19.70; S,11.27; Found: C, 63.07; H, 5.48; N, 19.71; S, 11.09.

EXAMPLE 5 Preparation of2-benzylthio-6-chloro-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 6.52 g (31.6 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 9.09 g (31.6 mmol) of 1,3-bis(dimethylamino)-2-chlorotrimethiniumperchlorate in 100 ml of glacial acetic acid was heated at reflux for 19hours. After cooling to room temperature, the solution was poured into300 ml of water. The solid which separated was collected by filtration,washed with water and dried in vacuo to yield 4.12 g (48%) fo thedesired product as a brown solid, m.p. 119.5°-135° C. (decomposition).IR and ¹ H NMR spectra were consistent with the assigned structure.

Analysis: Calculated for C₁₂ H₉ ClN₄ S: C, 51.90; H, 3.20; N, 20.24;Found: C, 51.87; H, 3.42; N, 19.81.

EXAMPLE 6 Preparation of 2-benzylthio-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 2.0 g (9.6 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 2.3 ml (9.6 mmol) of malonaldehyde bis(diethylacetal) in 20 ml ofglacial acetic acid was heated at reflux for 17 hours. After cooling toroom temperature, the solvent was removed by evaporation at reducedpressure. The brown solid residue was recrystallized from isopropylalcohol to afford 0.4 g (17%) of the desired product as a light browncrystalline solid, m.p. 104°-106° C. IR and ¹ H NMR spectra wereconsistent with the assigned structure.

Analysis: Calculated for C₁₀ H₁₂ N₄ S: C, 59.52; H, 4.13; N, 23.13.Found: C, 59.19; H, 4.09; N, 22.73.

EXAMPLE 7 Preparation of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of sodium ethoxide in EtOH was prepared by dissolving 0.54 g(24 mg-atoms) of sodium metal in 120 ml of anhydrous EtOH, and 10.0 g(48 mmol) of 3-amino-5-benzylthio-1,2,4-triazole was added. Afterstirring for 15 minutes at room temperature, 6.4 ml (6.35 g, 48.4 mmol)of acetylacetaldehyde dimethyl acetal dissolved in 100 ml of absoluteEtOH was added dropwise. After the addition was complete the reactionmixture was stirred at room temperature for 68 hours. The product whichseparated from solution was collected by filtration and dried to give10.1 g (83%) of tan solid, m.p. 128.5°-130° C. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ N₄ S: C, 60.94; H, 4.68; N, 21.86.Found: C, 60.69; H, 4.61; N, 21.85.

EXAMPLE 8 Preparation of2-benzylthio-5-hydroxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

Ethyl 2,3-dibromobutyrate (1.33 g, 48.5 mmol) was added dropwise over 15minutes to a solution of 10 g (49 mmol) of 3-amino-5-benzylthio-1,2,4-triazole in 20 ml of pyridine heated to 65° C. Afterthe addition was complete, the reaction mixture was heated at 65° C. for20 hours, cooled to room temperature and filtered. The filtrate wasconcentrated by evaporation at reduced pressure. The residue wastriturated with methanol to separate 1.64 g (13%) of the desired productas a colorless crystalline solid, m.p. 219°-220° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ N₄ OS: C, 57.37; H, 4.41; N, 20.60;Found: C, 56.86; H, 4.41; N, 20.72.

EXAMPLE 9 Preparation of2-benzylthio-5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 2.67 g (9.80 mmol) of2-benzylthio-5-hydroxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 50 mlof phosphorous oxychloride was heated at reflux for 3 hours. The excessphosphorous oxychloride was removed by evaporation at reduced pressure.The residue was partitioned between CH₂ Cl₂ and cold water. The organicphase was separated, dried (MgSO₄) and concentrated by evaporation atreduced pressure. The resulting solid was added to 50 ml (0.22 mol) of a25 weight percent solution of sodium methoxide in methanol. Theresulting suspension was stirred at room temperature for 30 minutes,diluted with 50 ml of water and filtered. The solid collected was driedin vacuo to yield 1.41 g (41%) of the desired product as a light brownsolid, m.p. 112.5°-115° C. IR and ¹ H NMR spectra were consistent withthe assigned structure.

EXAMPLE 10 Preparation of2-benzylthio-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 50 g (0.24 mol) of 3-amino-5-benzylthio-1,2,4-triazole in500 ml of glacial acetic acid was added dropwise over 3-4 hours to asolution of 34.0 g (0.25 mol) of acetylacetaldehyde dimethyl acetal in500 ml of glacial acetic acid heated at 100° C. After the addition wascomplete the reaction mixture was heated at reflux overnight, cooled toroom temperature and poured into an ice-water mixture. The solid whichseparated was collected by filtration and recrystallized from ethanol toyield 27 g (41%) of the desired product as a solid, m.p. 102°-104° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ N₄ S: C, 60.94; H, 4.68; N, 21.85;Found: C, 60.81; H, 4.68; N, 21.74.

EXAMPLE 11 Preparation of2-benzylthio-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A suspension of 14.4 g (0.124 mol) of 3-amino-5-benzyl-1,2,4-triazoleand 30.0 g (0.124 mol) of 1,3-bis(dimethylamino)-2-methyltrimethiniumperchlorate in 500 ml of glacial acetic acid was heated at reflux for 63hours. The reaction mixture was subjected to the work-up described inExample 5 to yield 13.9 g (68%) of the desired product as a brown solid,m.p. 254°-256° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₆ H₆ N₄ S: C, 43.35; H, 3.61; N, 33.72; Found:C, 42.71; H, 3.49; N, 33.26.

EXAMPLE 12 Preparation of2-benzylthio-6-chloro-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

To a suspension of 153 g (0.74 mol) 3-amino-5-benzylthio-1,2,4-triazolein 250 ml of glacial acetic acid was added to 100 g (0.74 mol) of3-chloro-2,4-pentanedione in a dropwise manner. The reaction mixture washeated at reflux for 18 hours and cooled to room temperature. Thereaction mixture was poured over ice and the oil which separatedsolidified upon stirring. The solid was collected by filtration andrecrystallized from methanol to yield 116 g (79%) of the desired productas an off white solid, m.p. 164°-166° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₃ ClN₄ S: C, 55.16; H, 4.30; N, 18.38;Found: C, 55.11; H, 4.30; N, 18.34.

EXAMPLE 13 Preparation of2-benzylthio-6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 28% yield from3-amino-5-benzylthio-1,2,4-triazole and1,3-bis(dimethylamino)-2-ethoxytrimethinium perchlorate following thegeneral procedure described in Example 5. The desired product wasisolated as a solid, m.p. 139°-140° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N, 19.57;Found: C, 58.68; H, 4.64; N, 19.58.

EXAMPLE 14 Preparation of2-benzylthio-5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 96% yield from3-amino-5-benzylthio-1,2,4-triazole and 4-methyl-3-oxopentanal followingthe general procedure described in Example 7. The desired product wasisolated as a solid, m.p. 65°-66° C. IR and ¹ H NMR were in agreementwith the assigned structure.

Analysis: Calculated for C₁₅ H₁₆ N₄ S: C, 63.36; H, 5.63; N, 19.71;Found: C, 63.00; H, 5.62; N, 19.62.

EXAMPLE 15 Preparation of2-benzylthio-5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 5.0 g (24 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and5.0 g (41 mmol) of the sodium salt of 2-methyl-3-oxobutanal in 200 ml ofglacial acetic acid was heated at reflux overnight. The solution wascooled to room temperature and the reaction mixture was concentrated byevaporation at reduced pressure. The residue was combined with ice andH₂ O to separate a tan solid. The solid was collected by filtration,dried and carefully recrystallized from ethyl acetate to yield 3.53 g(54%) of the desired product as a crystalline solid, m.p. 147°-149° C.IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₄ N₄ S: C, 62.10; H, 5.18; N, 20.72;Found: C, 61.58; H, 5.18; N, 20.45.

EXAMPLE 16 Preparation of2-benzylthio-6-chloro-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 16 g (77 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and10.6 g (77 mmol) of ethyl 2-chloroacetoacetate in 150 ml of glacialacetic acid was heated at 100° C. for 17 hours. Upon cooling to roomtemperature the solid which separated was collected by filtration. Thefiltrate was diluted with ice water to separate an additional quantityof solid. The solids were combined and dried to yield 14.0 g (60%) ofthe desired product as a solid, m.p. 258°-260° C. IR and ¹ H NMR were inagreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₁ ClN₄ OS: C, 50.89; H, 3.58; N, 18.27;Found: C, 50.51; H, 3.36; N, 18.67.

EXAMPLE 17 Preparation of2-benzylthio-6,7-dichloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 68% yield from2-benzylthio-6-chloro-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidineand phosphorus oxychloride following the general procedure described inExample 20. The desired product was isolated as a solid, m.p. 103°-105°C. IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₀ Cl₂ N₄ S: C, 48.00; H, 3.07; N, 17.23;Found: C, 47.40; H, 3.00; N, 17.43.

EXAMPLE 18 Preparation of2-benzylthio-6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared by reduction of2-benzylthio-6,7-dichloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine withzinc-copper couple following the general procedure described in Example21. The desired product was isolated in 88% yield as a solid, m.p.160°-161° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₁₃ H₁₁ ClN₄ S: C, 53.56; H, 3.56; N, 19.27;Found: C, 53.30; H, 3.79; N, 19.28.

EXAMPLE 19 Preparation of2-benzylthio-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 125 g (0.58 mol) of a 25% solution of sodium methoxide inmethanol dissolved in 100 ml of absolute ethanol was treated with 66.3ml (0.29 mol) of dimethyl malonate followed by 60.0 g (0.20 mol) of3-amino-5-benzylthio-1,2,4-triazole. The resulting solution was heatedat reflux for 5 days. On cooling to room temperature the solid which hadseparated was collected by filtration, washed with cold ethanol anddissolved in 1000 ml of water. The resulting yellow solution wasacidified with concentrated HCl to precipitate a solid. The solid wascollected by filtration and dried to yield 70.1 g (82%) of the desiredproduct as a white solid, m.p. 199°-210° C. (decompostion). IR and ¹ HNMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₂ H₁₀ N₄ O₂ S.H₂ O: C, 49.30; H, 4.14, N.19.16; Found: C, 48.70; H, 3.89; N. 18.83.

EXAMPLE 20 Preparation of2-benzylthio-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine

A suspension of 70.0 g (0.24 mol) of2-benzylthio-5,7-dihydroxyl-1,2,4-triazolo[1,5-a]pyrimidine and 67.0 ml(0.72 mol) of phosphorous oxychloride in 600 ml of acetonitrile washeated at reflux for 3 hours. The resulting orange solution was stirredat room temperature overnight (17 hours). The solution was filtered andthe filtrate was concentrated by evaporation at reduced pressure. Theresidue was partitioned between cold water and methylene chloride, andthe organic phase was separated and dried (MgSO₄). The organic phase wasconcentrated to induce crystallization. The desired product wascollected by filtration to yield 98.0 g (81%) of solid, m.p. 97°-100° C.IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₂ H₈ Cl₂ N₄ S: C, 46.32; H, 2.59; N, 18.00;Found: C, 46.43; H, 2.57; N, 18.08.

EXAMPLE 21 Preparation of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine

A zinc-copper couple was prepared following the procedure of Bradley (J.Org. Chem. 31, 626 (1966)) by stirring 1.0 g of copper sulfate in 20 mlof water with 15.0 g of zinc dust for 2 hours. The couple was collectedby filtration, washed with acetone and dried overnight under vacuum at100° C. To a solution of 33.0 g (106 mmol) of2-benzylthio-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine in 12.5 ml(213 mmol) of acetic acid, 50 ml of methanol and 300 ml oftetrahydrofuran was added 20.5 g of Zn--Cu couple. The mixture wasstirred overnight at 22°-23° C. When the reaction was complete (TLCanalysis) the reaction mixture was filtered through celite and thefiltrate was concentrated by evaporation at reduced pressure. Theresidue was triturated with hexane to separate a solid. The solid wascollected by filtration to yield the desired product as 26.5 g (92%) oforange solid, m.p. 125°-127° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis: Calculated for C₁₂ H₉ ClN₄ S: C, 52.08; H, 3.25; N, 20.25;Found: C, 51.76; H, 3.00; N, 20.27.

EXAMPLE 22 Preparation of2-benzylthio-5-methoxy-1,2,4-triazolo[1,5-a]pyrimidine

A mixture of 6.0 g (22 mmol) of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine in 25 ml ofmethanol was treated with 5.0 g (23.8 mmol) of a 25% solution of sodiummethoxide in methanol. After stirring for 1.5 hours the reaction mixturewas diluted with 100 ml of water and neutralized with 3N HCL (aq). Thesolid which separated was collected by filtration, washed with water anddried to afford 5.0 g (84%) of the desired product as a white solid,m.p. 126°-128° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₁₃ H₁₂ N₄ OS: C, 57.34; H, 4.41; N, 20.58;Found: C, 57.21; H, 4.42; N, 20.13.

EXAMPLE 23 Preparation of2-benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-]pyrimidine

A solution of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran wasprepared by the addition of 1.1 g (48 mg-atom) of sodium metal to asolution of 3.5 ml (48 mmol) of 2,2,2-trifluoroethanol in 100 ml oftetrahydrofuran. To this solution was added 7.0 g (25 mmol) of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine, and the reactionmixture was stirred for 30 minutes and concentrated by evaporation atreduced pressure to approximately one quarter of the original volume.Pentane (200 ml) was added to induce crystallization. The solid whichseparated was collected by filtration to yield 6.42 g (75%) of thedesired product as a light yellow wolid, m.p. 114°-118° C. IR and ¹ HNMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₁ F₃ N₄ OS: C, 49.40; H, 3.23; N, 16.46;Found: C, 49.63; H, 3.09; N, 16.70.

EXAMPLE 24 Preparation of2-benzylthio-5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared by heating2-benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidinein boiling ethanol. The hot mixture was filtered and the filtrate wasconcentrated. The crude product was recrystallized from isopropanol toyield the desired product as a solid, m.p. 115°-117° C. IR and ¹ HNMRspectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N, 19.31; S,11.20; Found: C, 57.90; H, 4.69; N, 19.30; S, 10.79.

EXAMPLE 25 Preparation of2-benzylthio-5,7-dihydroxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 80% yield from3-amino-5-benzylthio-1,2,4-triazole and dimethyl 2-methyl malonatefollowing the general procedure described in Example 19. The product wasisolated as a solid, m.p. 260°-272° C. (decomposition). IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ N₄ O₂ S: C, 54.15; H, 4.16; N, 19.44;Found: C, 53.48; H, 4.07; N, 19.53.

EXAMPLE 26 Preparation of2-benzylthio-5,7-dichloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 97% yield from the reaction of2-benzylthio-5,7-dihydroxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine andphosphorous oxychloride following the general procedure described inExample 20. The product was isolated as a solid, m.p. 121°-123° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₀ Cl₂ N₄ S: C, 48.01; H, 3.08; N, 17.23;Found: C, 47.65; H, 3.11; N, 17.70.

EXAMPLE 27 Preparation of2-benzylthio-5-chloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 32% yield by reduction of2-benzylthio-5,7-dichloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine withzinc-copper couple following the general procedure described in Example21. The desired product was isolated as a solid, m.p. 179°-181° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₁ ClN₄ S: C, 53.70; H, 3.79; N, 19.28;Found: C, 53.33; H, 3.73; N, 19.53.

EXAMPLE 28 Preparation of2-benzylthio-5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 64% yield by reaction of2-benzylthio-5-chloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine withsodium methoxide following the general procedure described in Example22. The desired product was isolated as a solid, m.p. 145°-146° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N. 19.58;Found: C, 58.34; H. 4.84; N, 19.67.

EXAMPLE 29 Preparation of2-benzylthio-6-ethoxycarbonyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 15 g (73 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and15.0 g (80.0 mmol) of ethyl ethoxymethyleneacetoacetate in 250 ml ofglacial acetic acid was heated at reflux for 60 hours. After cooling thevolume of the reaction was reduced to approximately one quarter of theoroginal volume by evaporation at reduced pressure. The resultingresidue was poured into water, and the solid which separated wascollected by filtration, washed with water and dried to yield 7.88 g(33%) of the desired product as a solid, m.p. 98°-99° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ N₄ O₂ S: C, 58.52; H, 4.87; N, 17.07;Found: C, 58.81; H, 4.89; N. 17.03.

EXAMPLE 30 Preparation of2-benzylthio-6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared from 3-amino-5-benzylthio-1,2,4-triazole and1,3-bis(dimethylamino)-2-(4-nitrophenyl)-trimethinium perchloratefollowing the general procedure described in Example 5. The desiredproduct was isolated as a solid, m.p. 195°-199° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

EXAMPLE 31 Preparation of2-benzylthio-5,6-cyclopentano-7-hydroxy-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.6 g (100 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 15 ml (16 g, 0.10 mol) of 2-carboethoxycyclopentanone in 110 ml ofglacial acetic acid was heated at reflux for 23 hours. After cooling toroom temperature the solid which separated from the reaction mixture wascollected by filtration, washed with acetic acid and dried in vacuo toyield 22.4 g (75%) of the desired product as a colorless crystallinesolid, m.p. 241°-243° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis: Calculated for C₁₅ H₁₄ N₄ OS: C, 60.38; H, 4.73; N, 18.78; S,10.75; Found: C, 60.10; H, 4.66; N, 18.91; S, 10.72.

EXAMPLE 32 Preparation of2-benzylthio-7-chloro-5,6-cyclopentano-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 5.97 g (20.0 mmol) of2-benzylthio-5,6-cyclopentano-7-hydroxy-1,2,4-triazolo[1,5-a]pyrimidinein 250 ml of phosphorus oxychloride was heated at reflux for 50 minutes.After cooling to room temperature the excess phosphorus oxychloride wasremoved by distillation at aspirator pressure. The residue waspartitioned between ice cold water and methylene chloride. The organicphase was dried (Na₂ SO₄) and evaporated at reduced pressure. Theresidue was chromatographed on silica gel eluting with EtOAc-hexane(1:1, v/v) to yield 3.72 g (59%) of the desired product as a yellowsolid, m.p. 119°-120° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis: Calculated for C₁₅ H₁₃ ClN₄ S: C, 56.87; H, 4.14; N, 17.68;Cl, 11.19; S, 10.12; Found: C, 56.91; H, 4.06; N, 17.83; Cl, 10.68; S;9.65.

EXAMPLE 33 Preparation of2-benzylthio-5,6-cyclopentano-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 2.47 g (7.80 mmol) of2-benzylthio-7-chloro-5,6-cyclopentano-1,2,4-triazolo[1,5-a]pyrimidinein 40 ml of dry tetrahydrofuran was cooled to 5° C. and 5.9 ml (17 mmol)of 2.9M methyl magnesium bromide in ether was added over 5 minutes.After the addition was complete the reaction mixture was warmed to roomtemperature and stirred overnight (17 hours). The reaction was quenchedby addition of 10 ml of saturated aqueous ammonium chloride. The organicphase was separated, dried (Na₂ SO₄) and evaporated at reduced pressure.The red oil residue was chromatographed on silica gel (HPLC) elutingwith EtOAc-hexane (1:1, v/v) to yield 1.12 g (48%) of the desiredproduct as a pale red solid, m.p. 109°-111° C. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ N₄ S: C, 64.84; H, 5.44; N, 18.90; S,10.82; Found: C, 64.99; H, 5.41; N. 18.16; S, 10.42.

EXAMPLE 34 Preparation of2-benzylthio-5,7-bis-(trifluoromethyl)-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.8 g (0.100 mol) of1,1,1,5,5,5-hexafluoro-2,4-pentanedione and 20.6 g (0.100 mol) of3-amino-5-benzylthio-1,2,4-triazole in 150 ml of glacial acetic acid washeated at reflux for 14 hours. The solution was cooled to roomtemperature and poured over ice. The solid which separated was collectedby filtration, washed with water and dried in vacuo to yield 35.5 g(94%) of the desired product as a pale yellow solid, m.p. 78.5°-80.5° C.IR, ¹ H NMR and ¹⁹ F NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₁₄ H₈ F₆ N₄ S: C, 44.45; H, 2.13; N, 14.81; S,8.48; Found: C, 44.53; H, 2.15; N, 14.97; S, 8.39.

EXAMPLE 35 Preparation of2-benzylthio-5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 84% yield from3-amino-5-benzylthio-1,2,4-triazole and 1,1,1-trifluoro-2,4-pentanedionefollowing the general procedure described in Example 34. The product waspurified by recrystallization from benzene-hexane to yield a tan solid,m.p. 83.5°-84.5° C. IR, ¹ H NMR and ¹⁹ F NMR spectra were in agreementwith the assigned structure.

Analysis: Calculated for C₁₄ H₁₁ F₃ N₄ S: C, 51.85; H, 3.42; N, 17.27;S, 9.89; Found: C, 51.73; H, 3.44; N, 18.01; S, 10.08.

EXAMPLE 36 Preparation of2-benzylthio-5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 8.40 g (37.5 mmol) of dibenzoylmethane and 7.73 g (37.5mmol) of 3-amino-5-benzylthio-1,2,4-triazole in 50 ml of glacial aceticacid was heated at reflux for 24 hours. Upon cooling to room temperaturethe solid which separated was collected by filtration and dried. Theproduct was chromatographed on silica gel (HPLC) eluting withEtOAc-hexane (3:7, v/v) to afford 5.08 g (34%) of the desired product asa colorless solid, m.p. 122.5°-123.5° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₂₄ H₁₈ N₄ S: C, 73.07; H, 4.60; N, 14.20; S,8.13; Found: C, 73.48; H, 4.54; N, 14.17; S, 7.97.

EXAMPLE 37 Preparation of2-benzylthio-5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine and2-benzylthio-7-methyl-5-phenyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.6 g (100 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 16.2 g (100 mmol) of benzoyl acetone in 100 ml of glacial aceticacid was heated at reflux for 14 hours. The solvent was removed byevaporation at reduced pressure and the residue was chromatographed onsilica gel (HPLC) eluting with EtOAc-hexane (3:7, v/v) to afford 4.81 g(14%) of 2-benzylthio-7-methyl-5-phenyl-1,2,4-triazolo[1,5-a]pyrimidineas a pale yellow wolid, m.p. 154°-155° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₉ H₁₆ N₄ S: C, 68.65; H, 4.85; N, 16.85; S,9.65; Found: C, 68.76; H, 4.82; N, 16.98; S, 9.93.

Further elution afforded 22.8 g (69%) of2-benzylthio-5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine as a paleyellow solid, m.p. 110°-111° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis: Calculated for C₁₉ H₁₆ N₄ S: C, 68.65; H, 4.85; N, 16.85; S,9.65; Found: C, 68.52; H, 4.75; N. 16.93; S, 9.61.

EXAMPLE 38 Preparation of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

Chlorine was bubbled into a suspension of 99.0 g (0.366 mol) of2-benzylthio-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine in 700 ml ofHOAc--H₂ O (1:1, v/v) cooled to -1° C. During the course of the additionthe temperature of the reaction mixture was maintained below 5° C. After2.5 hours the chlorine addition was ceased and the reaction mixture wasfiltered to collect a tan solid. The filtrate was diluted with H₂ O toseparate an additional quantity of solid which was collected byfiltration. The combined solid products were dried in vacuo to yield70.4 g (78%) of crude sulfonyl chloride III (X═Z═Me, Y═H) as a tansolid. IR and ¹ HNMR spectra confirmed the structure.

Recrystallization from EtOAc produced an analytical sample as anoff-white solid, m.p. 128.5°-130.5° C.

Analysis: Calculated for C₇ H₇ ClN₄ O₂ S: C, 34.09; H, 2.86; N, 20.73;S, 13.00; Found: C, 34.34; H, 2.80; N, 22.64; S, 12.85.

EXAMPLE 39 Preparation of6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

Chlorine gas was bubbled into a suspension of 4.45 g (15.0 mmol) of2-benzylthio-6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidinein 30 ml of HOAC--H₂ O (1:1, v/v) cooled to -4° C. After 30 minutes theaddition was stopped and the reaction mixture was stirred for 30 minutesmaintaining the temperature below 5° C. The reaction mixture wasfiltered and the collected solid was dried under vacuum to yield 3.46 g(85 percent) of the desired sulfonyl chloride as a cream colored solidwhich was used directly without further purification: IR (CHCl₃) 1627,1551, 1398 and 1170 cm⁻¹ ; ¹ H NMR (CDCl₃) δ3.50 (2H, broad t), 3.18(2H, broad t) and 2.2-2.8 (5H, m including s at 2.68).

EXAMPLE 40 Preparation of5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

Chlorine was bubbled into a suspension of 28.4 g (0.100 mol) of2-benzylthio-5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine in 200 mlof glacial acetic acid--H₂ O (1:1, v/v) and cooled to -5° C. Thechlorine addition continued over 35 minutes and the temperature of thereaction mixture never exceeded 5° C. After the addition was complete,the reaction mixture was stirred for 5 minutes and filtered. The solidcollected was washed twice with H₂ O and dried in vacuo to yield 24.3 g(93%) of the crude sulfonyl chloride as a pale yellow solid. The IR and¹ H NMR were consistent with the assigned structure. The crude sulfonylchloride was used in subsequent transformations without furtherpurification.

EXAMPLE 41 Preparation of6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 3.75 g (13.5 mmol) of2-benzylthio-6-chloro-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH--H₂ O (1:1, v/v) was cooled to -10° C. and chlorine gas was bubbledinto the reaction mixture for 10 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes and dilutedwith 25 ml of H₂ O. The mixture was filtered and the filtrate wasextracted with CH₂ Cl₂. The organic phase was evaporated at reducedpressure to afford 2.14 g of the crude sulfonyl chloride as a liquid. IRand ¹ H NMR spectra were in agreement with the assigned structure.

EXAMPLE 42 Preparation of 1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

A suspension of 8.0 g (33 mmol) of2-benzylthio-1,2,4-triazolo[1,5-a]pyrimidine in 60 ml of HOAc--H₂ O(1:1, v/v) was cooled below 0° C. and chlorine gas was bubbled into thereaction mixture for 15 minutes. The temperature of the reaction mixturewas maintained below 10° C. during the course of the addition. After theaddition was complete, the reaction mixture was stirred for 15 minutes,diluted with H₂ O and extracted with CH₂ Cl₂. The organic phase wasdried (MgSO₄) and evaporated at reduced pressure to yield 5.74 g of thedesired crude product as a brown oil. IR and ¹ H NMR were in agreementwith the assigned structure.

Recrystallization from EtOAc gave an analytical sample, m.p. 105°-109°C.

Analysis: Calculated for C₅ H₃ ClN₄ O₂ S: C, 27,45; H, 1.32; N, 25.62;Found: C, 28.91; H, 1.52; N, 25.79.

EXAMPLE 43 Preparation of5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

A suspension of 2.77 g (10.8 mmol) of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH--H₂ O (1:1, v/v) was cooled to -10° C. and chlorine gas was bubbledinto the solution for 10 minutes. After the addition was complete, thereaction mixture was stirred for 5 minutes, diluted with H₂ O (25 ml)and filtered. The solid collected was dried in vacuo to yield 1.17 g ofthe desired sulfonyl chloride. IR and ¹ H NMR were in agreement with theassigned structure.

An additional quantity of the product contaminated with by-productscontaining benzyl residues was obtained by extraction of the filtratewith CH₂ Cl₂ and evaporation of the organic phase at reduced pressure.

EXAMPLE 44 Preparation of5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 1.41 g (4.93 mmol) of2-benzylthio-5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 mlof AcOH--H₂ O (1:1, v/v) was cooled to -20° C., and chlorine gas wasbubbled into the reaction mixture for 5 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes, diluted withH₂ O (20 ml) and filtered. The solid collected was dried in vacuo toyield 0.63 g of the desired crude sulfonyl chloride as a colorlesssolid. IR and ¹ H NMR were in agreement with the assigned structure.

EXAMPLE 45 Preparation of7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 3.52 g (13.7 mmol) of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH--H₂ O (1:1, v/v) was cooled to -10° C., and chlorine gas wasbubbled into the reaction mixture for 10 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes, diluted withH₂ O and filtered. The solid collected was dried in vacuo to yield 0.46g of the desired sulfonyl chloride as a tan solid. IR and ¹ H NMRspectra were in agreement with the assigned structure.

An additional quantity (2.2 g) of crude sulfonyl chloride contaminatedwith by-products containing benzyl residues was obtained by extractionof the filtrate with CH₂ Cl₂ and evaporation at reduced pressure.

EXAMPLE 46 Preparation of6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 10.0 (60 mmol) of2-benzylthio-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 260 ml ofmethylene chloride, 100 ml of water and 17 ml of concentrated HCl wascooled to -5° C. and treated with 284 ml (197 mmol) of 5.25% aqueoussodium hypochlorite (commercial bleach) by dropwise addition. After theaddition was complete the reaction mixture was stirred for 20 minutes at0° C. and filtered. The organic layer was separated and the aqueouslayer was extracted twice with methylene chloride. The combined organicphases were dried (MgSO₄) and evaporated at reduced pressure to yield7.0 g (50%) of the desired product as a solid, m.p. 106°-108° C. IR and¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₆ H₅ ClN₄ O₂ S: C, 30.96; H, 2.15; N, 24.08;Found: C, 31.00; H, 2.23; N, 23.91

EXAMPLE 47 Preparation of6-chloro-5,7-dimethyl-1,2,4-triazol[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 50% yield from2-benzylthio-6-chloro-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidinefollowing the general procedure described in Examples 38-45. The productwas isolated as a pale yellow solid, m.p. 131°-133° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

EXAMPLE 48 Preparation of6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 82% yield from2-benzylthio-6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid m.p. 134°-137° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis: Calculated for C₇ H₇ ClN₄ O₃ S: C, 31.96; H, 2.66; n, 21.31;Found: C, 32.64; H, 2.36; N, 21.30.

EXAMPLE 49 Preparation of5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 56% yield from2-benzylthio-5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Example 46. The product was isolated as asolid, m.p. 60°-62° C. IR and 1¹ HNMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₈ H₉ ClN₄ O₂ S: C, 36.85; H, 3.45; N, 21.49;Found: C, 37.02; H, 3.49; N, 21.71.

EXAMPLE 50 Preparation of5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 80% yield from2-benzylthio-5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Example 46. The product was isolated as asolid, m.p. 116°-120° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Exact mass calculated for C₇ H₇ ClN₄ O₂ S: 245.9984; Found: 245.9981.

EXAMPLE 51 Preparation of6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 60% yield from2-benzylthio-6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine followingthe general procedure described in Examples 38-45. The product wasisolated as a solid, m.p. 99°-101° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

EXAMPLE 52 Preparation of5-methoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 57% yield from2-benzylthio-5-methoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid, m.p. 110°-112° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis: Calculated for C₆ H₅ ClN₄ O₃ S: C, 28.97; H, 2.01: N, 22.53;Found: C, 29.90; H, 2.23; N, 22.76.

EXAMPLE 53 Preparation of5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

This material was prepared in 74% yield from2-benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidinefollowing the general procedure described in Examples 38-45. The productwas isolated as a solid, m.p. 91°-96° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Exact mass calculated for C₇ H₄ ClF₃ N₄ O₃ S: 315.9655; Found: 315.9650.

EXAMPLE 54 Preparation of5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 74% yield from2-benzylthio-5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid, m.p. 91°-96° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

EXAMPLE 55 Preparation of5-methoxy-6-methyl-1,2,4triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 80% yield from2-benzylthio-5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidinefollowing the general procedure outlined in Examples 38-45. The productwas isolated as a solid, m.p. 154°-157° C. IR and ¹ H NMR spectra werein agreement with the assigned structure.

Analysis: Calculated for C₇ H₇ ClN₄ O₃ S: C, 32.00; H, 2.67; N, 21.33;Found: C, 32.35; H, 2.61; N, 21.45.

EXAMPLE 56 Preparation of6-ethoxycarbonyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

This material was prepared in 82% yield from2-benzylthio-6-ethoxycarbonyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidinefollowing the general procedure described in Example 46. The product wasisolated as a solid, m.p. 65°-69° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₉ H₉ ClN₄ O₄ S: C, 35.47; H, 2.95; N, 18.39;Found: C, 36.04; H, 3.02; N, 18.27.

EXAMPLE 57 Preparation of6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 71% yield from2-benzylthio-6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine followingthe general procedure described in Examples 38-45. The product wasisolated as a solid, m.p. 159°-167° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

EXAMPLE 58 Preparation of5,7-dimethyl-N-(2-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

To a solution of 0.74 ml (0.90 g, 7.0 mmol) of o-chloroaniline in 10 mlof dry pyridine was added 1.89 g (7.66 mmol) of the sulfonyl chlorideprepared in Example 1. The resulting dark solution was stirred atambient temperature for 18 hours and evaporated to dryness. The residuewas treated with 15 ml of 1N NaOH and charcoal stirred for 15 minutes.The mixture was filtered through celite and the filtrate was acidifiedwith 3N HCl to precipitate the product. Filtration and drying in vacuogave the desired product (2.01 g, 85%) as a light brown solid, m.p.188°-189.5° C. IR and ¹ H NMR spectra were in agreement with the desiredstructure I (Ar=o-chlorophenyl, X═Z═Me, Y═H).

Analysis: Calculated for C₁₃ H₁₂ ClN₅ O₂ S: C, 46.23; H, 3.58; N, 20.73;Cl, 10.50; S, 9.49; Found: C, 46.09; H, 3.58; N, 20.89; Cl, 10.34; S,9.37.

EXAMPLE 59 Preparation of methylN-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate

To a solution of 0.91 ml (1.1 g, 7.0 mmol) of methyl anthranilate in 10ml of dry pyridine was added 1.89 g (7.66 mmol) of the sulfonyl chlorideprepared in Example 1. The resulting dark solution was stirred at roomtemperature for 18 hours and evaporated to dryness. The residue wastreated with 15 ml of 1N NaOH and charcoal and stirred for 15 minutes.The mixture was filtered through celite, and the filtrate was acidifiedwith 3N HCl to precipitate the product. The product was collected byfiltration and dried in vacuo to yield 2.27 g (90%) of the desiredproduct I (X═Z═Me, Y═H, Ar=o-carbomethoxyphenyl) as a cream coloredsolid, m.p. 169.5°-170.5° C. IR and ¹ H NMR spectra confirmed thestructure of the product.

Analysis: Calculated for C₁₅ H₁₅ N₅ O₄ S: C, 49.86; H, 4.18; N, 19.38;S, 8.87; Found: C, 49.68; H, 4.13; N, 19.35; S, 8.69.

EXAMPLE 60 Preparation of5,7-dimethyl-N-(2,6-dimethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 2.2. g (8.9 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride, 1.01ml (8.4 mmol) of 2,6-dimethylaniline, 0.7 ml (8.4 mmol) of dry pyridineand 4 mg of DMAP in 20 ml of CH₂ Cl₂ was stirred at room temperature for17 hours. The solvent was removed by evaporation and the residue wastaken up in 0.5M NaOH. The solution was extracted with diethyl ether andthe aqueous phase was acidified with 3N HCl to precipitate a solid. Thesolid was collected by filtration and dried in vacuo to yield 2.72 g (97percent) of the desired product as a white solid, m.p. 263°-266° C.(decomp.): ¹ H NMR (DMSO-d₆) δ10.4 (1H, broad S), 7.55 (1H, s), 7.2 (3H,s), 2.7 and 2.8 (3H each, s) and 2.1 (6H, s); IR (KBr) 3100, 2980-2780,1628, 1540 and 1355 cm⁻¹.

Analysis: Calculated for C₁₅ H₁₇ N₅ O₂ S: C, 54,31; H, 5.23; N, 21.23;Found: C, 53.59; H, 5.07; N, 20.65.

EXAMPLE 61 Preparation of6,7-cyclopentano-5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 3.31 g (12.1 mmol) of crude6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride and 1.87 g (11.6 mmol) of 2,6-dichloroaniline in 15 ml of drypyridine was stirred at 45°-50° C. for 23 hours. The majority of thepyridine was removed by evaporation at reduced pressure, and the residuewas treated with 25 ml of 1N NaOH and ice. After stirring for 15minutes, the mixture was filtered and the filtrate was acidified with 3NHCl to precipitate a light brown solid. The solid was taken up in 0.5NNaOH and filtered. The filtrate was acidified with 3N HCl to precipitatea solid. The solid was collected by filtration and dried in vacuo toyield 1.19 g (26 percent) of the desired sulfonamide as a light brownsolid, m.p. 264°-266° C.: ¹ H NMR (DMSO-d₆) δ10.83 (1H, broad s), 7.1-7.6 (3H, m) and 2.0-3.6 (9H, m including s at 2.57); IR (KBr) 3410,1620, 1549, 1442, 1399, 1358 and 1167⁻¹.

Analysis: Calculated for C₁₅ H₁₃ Cl₂ N₅ O₂ S: C, 45.24; H, 3.29; N,17.58; Found: C, 45.47; H, 3.18; N, 17.41.

EXAMPLE 62 Preparation of5,7-dimethyl-N-(2,4,6-trichlorophynyl)-1,2,4-trizaolo[1,5-a]pyrimidine-2-sulfonamide

A solution (10.7 ml, 17.1 mmol) of 1.60M N-butyllithium in hexane wasadded to a solution of 3.20 g (16.3 mmol) of 2,4,6-trichloroaniline in20 ml of dry THF cooled to -78° C. The resultant solution was thenallowed to warm to room temperature. This solution was added to asolution of 2.00 g (8.11 mmol) of5,7-dimethyl-1,2,4-triazolo[1,4-a]pyrimidine-2-sulfonyl chloride in 30ml of dry THF cooled to -10° C. The temperature of the reaction mixturewas maintained between -13° C. and -9° C. during to course of theaddition. After the addition was complete, the reaction mixture wasstirred for 30 minutes and warmed to room temperature. After 1 hour atroom temperature, THF was removed from the reaction mixture byevaporation. The residue was triturated with H₂ O and filtered. Thefiltrate was treated with charcoal and filtered through celite. Thefiltrate was washed with Et₂ O, and the aqueous phase was separated andacidified with 3N HCl to precipitqte a solid. The solid was collected byfiltration, washed with water and dried in vacuo to yield 0.70 g (21%)of the desired product as a tan solid, m.p. >200° C. (decomp.) ¹ H NMRand IR spectra were consistent with the assigned structure.

Analysis: Calculated for C₁₃ H₁₀ N₅ O₂ S: C, 38.40; H, 2.48; N, 17.22;Found: C, 38.36; H, 2.48; N, 17.14.

EXAMPLE 63 Preparation of6-chloro-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

The starting 2,6-difluoroaniline (1.7 g, 13 mmol) was dissolved in 3.5ml of pyridine and 3.5 g (14 mmol) of6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride was added.After an exothermic reaction subsided the reaction mixture was heated at60°-70° C. overnight. The solvent was removed by evaporation at reducedpressure and the residue was taken up in aqueous sodium bicarbonate. Theaqueous solution was washed with ether, and acidified with acqueous HCl.The solid which separated upon acidification was collected byfiltration, dried and recrystallized from methanol to afford 2.5 g (55%)of the desired product as a crystalline solid, m.p. 224°-226° C. IR and¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₁ H₆ ClF₂ N₅ O₂ S: C, 38.21; H, 1.75; N,20.26; Found: C, 38.32; H, 1.44; N, 20.18.

EXAMPLE 64 Preparation of methyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate

Methyl 3-methylanthranilate (2.1 g, 13 mmol) was dissolved in 4 mlpyridine and 6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride was added. After a mild exothermic reaction subsided thereaction mixture was stirred at 50° C. for 24 hours. The pyridine wasremoved by evaporation at reduced pressure and the residue was treatedwith in 10% aqueous sodium bicarbonate. Insouble material was collectedby filtration, washed with ether and dried to yield 2.9 (63%) of thedesired product as a solid, m.p. 198.5°-205° C. An analytical sample wasprepared by recrystallization from ethanol to yield a crystalline solid,m.p. 208.5°-210.5° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₁₅ H₁₅ N₅ O₄ S: C, 49.85; H, 4.18; N, 19.38;Found: C, 49.96; H, 4.14; N, 19.75.

EXAMPLE 65 Preparation of5-methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

The starting 2,6-difluoroaniline (18.1 g, 0.140 mol) was dissolved in 45ml of pyridine and 36.1 g (0.155 mol) of5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride was added.After an exothermic reaction subsided the reaction mixture was stirredat room temperature for 15.5 hours. The pyridine was removed byevaporation at reduced pressure, and the residue was treated with 600 mlof 0.5N naOH. After stirring to dissolve all soluble material themixture was filtered through celite and the filtrate was acifified with3N HCl. The precipitate which separated upon acidification was collectedby filtration and dried to yield 33.0 g (73%) of the desired product asa pale red solid, m.p. 245°-247° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₂ H₉ F₂ N₅ O₂ S: C, 44.31; H, 2.79; N, 21.53;Found: C, 44.69; H, 2.80; N, 21.85.

EXAMPLE 66 Preparation of5,7-dimethyl-N-(2-acetoxymethyl-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 1.30 gm (6.50 mmol) of 2-amino-3-chlorobenzyl acetate,4.11 gm (52.0 mmol) of pyridine and 5.0 ml of acetonitrile was treatedwith 1.61 gm (6.50 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride and theresulting mixture stirred at 25° C. for 120 hours. An additional 0.53 gm(2.2 mmol) of the sulfonyl chloride was added and stirring at 25° C.continued for an additional 24 hours. The mixture was filtered and thefiltrate evaporated to provide a brown oil. The oil was then dissolvedin 40 ml of m ethylene chloride and stirred with 25 ml of 0.5M NaOH.After 5 minutes, the aqueous phase was separated, washed with ether andacidified with 3N HCl. A light brown solid was collected, washed withwater, dried and recrystallized from acetonitrile to provide 0.35 gm(13%) of the desired product as a solid, m.p. 214°-217° C., containingapproximately 10% of an impurity. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ ClN₅ O₄ S: C, 46.89; H, 3.94; N, 17.08;Found: C, 46.60; H, 3.80, N, 17.73.

EXAMPLE 67 Preparation of methyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoate

A solution of 1.50 g (6.15 mmol) of methyl2-bromo-3-amino-4-methylbenzoate in 7 ml of pyridine was treated with1.67 g (6.76 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl chloride. Afterstirring at 25° C. for 18 hours an additional 0.46 g (1.9 mmol) of thesulfonyl chloride was added and the reaction mixture was heated at52°-55° C. for 3 hours. The solvent was removed by evaporation and theresidue was partitioned between methylene chloride and dilute aqueousHCl. The organic phase was washed with water, dried and evaporated atreduced pressure to yield 1.85 g (66%) of the desired product as ayellow solid upon trituration with ethyl acetate. An analytical samplewas prepared by recrystallization from acetonitrile-DMF to afford acrystalline solid, m.p. 229°-231° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ BrN₅ O₄ S: C, 42.30; H, 3.55; N, 15.41;Found: C, 42.29; H, 3.45; N, 15.68.

EXAMPLE 68 Preparation of3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoicacids

A solution of 2.78 g (6.12 mmol) of methyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoateand 30 ml of 5% aqueous NaOH in 30 ml of water was stirred at 25° C. for2.5 hours. The reaction mixture was filtered and the filtrate was cooledin ice and acidified to approximately pH 2 with 3N HCl. The solid whichseparated was collected by filtration, washed with water and dried invacuo to yield 2.10 g (78%) of the desired product as a gold solid, m.p.290° C. (decomposition). IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis: Calculated for C₁₅ H₁₄ BrN₅ O₄ S: C, 40.92; H, 3.21; N, 15.90;Found: C, 40.51; H, 3.11; N, 16.01.

EXAMPLE 69 Preparation of5-methylthio-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

To 25 ml (13 mmol) of a 0.52M solution of sodium methyl mercaptide inDMSO prepared by bubbling methyl mercaptan into a suspension of sodiumhydride in DMSO, was added 2.6 g (5.9 mmol) of5-(2,2,2-trifluoroethoxy)-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide.The solution was stirred at room temperature for 25 hours, diluted with100 ml of ice water and neutralized with 3N aqueous HCl. The gummy solidwhich separated was collected and taken up in 0.5N aqueous NaOH. Themixture was filtered to remove insoluble material, and the filtrate wasacidified with 6N aqueous HCl. The solid which separated was collectedby filtration and dried to yield 1.5 g (66%) of the desired product as apale yellow solid, m.p. 239°-243° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₂ H₉ Cl₂ N₂ O₂ S₂ : C, 36.92; H, 2.31; N,17.95; Found: C, 36.51; H, 2.41; N, 17.68.

EXAMPLE 70 Preparation of5-dimethylamino-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfon-amide

The starting5-(2,2,2-trifluoroethoxy)-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide(1.5 g, 3.4 mmol) was dissolved in 5 ml (44 mmol) of 50% aqueousdimethylamine. After stirring for 48 hours at room temperature thesolution was diluted with water and acidified with 6N aqueous HCl. Thesolid which separated was collected by filtration and treated with 0.5Naqueous NaOH and filtered to remove insoluble material. The filtrate wasacidified to precipitate a solid. The solid was collected and dried toyield 1.0 g (60%) of the desired product as a solid, m.p. >310° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ Cl₂ H₆ O₂ S: C, 40.31; H, 3.10; N,21.71; S, 8.28; Found: C, 40.08; H, 3.05; N, 22.33 S, 7.99.

EXAMPLE 71 Preparation of6-bromo-5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A suspension of 4.0 g (11 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidein 50 ml of glacial acetic acid and 10 ml of acetic anhydride wasstirred at 90° C. for 30 minutes. N-Bromosuccinimide (2.4 g, 13 mmol)was added to this hot solution, and the reaction mixture was stirred at90° C. for 60 minutes. The solution was cooled and poured into 200 ml ofice water. A solid which separated was collected and dried. This crudeproduct was purified by dissolving the sample in methylene chloride,filtering the solution through silica gel and triturating the fitratewith pentane. The desired product was obtained as a solid, m.p.215°-216° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Exact mass calculated for C₁₂ H₈ BrCl₂ N₅ O₂ S: 438.8898; Found:438.8899.

EXAMPLE 72 Preparation of5,7,N-trimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A mixture of 3.00 g (8.06 mmol) of5,7-dimethyl-1,N-(2,6-dichlorophenyl)-2,4-triazolo[1,5-a]pyrimidine-2-sulfonamideand 0.90 g (8.1 mmol) of potassium t-butoxide in 30 ml of acetonitrilewas heated at reflux for 40 minutes. After cooling to room temperature1.14 g (8.06 mmol) of methyl iodide were added, and the reaction washeated at reflux for 1 hour. After cooling to room temperature, thereaction mixture was diluted with methylene chloride and washed with 1%aqueous NaOH. The organic phase was spearated, dried (MgSO₄) andevaporated at reduced pressure. The brown solid residue wasrecrystallized from acetone to give 1.60 g (51%) of the desire productas a tan solid, m.p. 220°-222° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₄ H₁₃ Cl₂ N₅ O₂ S: C, 43.54; H, 3.39; N,18.13; Found: C, 43.55; H, 3.32; N, 18.03.

EXAMPLE 73 Preparation of5-methyl-N-benzoly-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A mixture of 3.00 g (8.37 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamideand 1.16 g (8.37 mmol) of anhydrous powdered K₂ CO₃ in 100 ml of acetonewas heated at reflux for 30 minutes. A solution of 1.18 g (8.37 mmol) ofbenzoyl chloride in 10 ml of acetone was added, and the reaction washeated at reflux for 115 min. The reaction was filtered, and thefiltrate was evaporated at reduced pressure. The solid residue wascollected by filtration, washed thoroughly with aqueous NaHCO₃ and H₂ Oand dried to yield 2.75 g (72%) of the desired product as a solid, m.p.187°-189° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₁₉ H₁₃ Cl₂ N₅ O₃ S: C, 49.36; H, 2.83; N,15.15; Found: C, 48.97; H, 2,84; N, 15.16.

EXAMPLE 74 Preparation of5-methyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium borohydride (0.6 g, 16 mmol) was added to a solution of 3.0 g(8.3 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidein 25 ml of dry DMSO. An exothermic reaction occured and 2.0 ml (31mmol) of methane sulfonic acid in 5 ml of DMSO was added at a rate tomaintain the temperature of the reaction mixture at 60° C. After theaddition was complete the reaction mixture was stirred for 10 minutesand carefully quenched with 0.5N aqueous NaOH. The clear yellow solutionwas filtered, and the filtrate was acidified with 3N aqueous HCl. Theresulting precipitate was treated with dilute aqueous NaOH and filteredto remove insoluble material. The filtrate was acidified with aqueousHCl to precipitate a solid. The solid was collected by filtration anddried to yield 1.11 g (37%) of the desired product as a solid, m.p.230°-235° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₁₂ H₁₂ Cl₂ N₅ O₂ S: C, 39.89; H, 3.32; N,19.39; Found: C, 39.72; H, 3.42; N, 19.19.

EXAMPLE 75 Preparation of methyl 3-amino-2,4-dichlorobenzoate

This material was prepared by chlorination of methyl3-amino-4-chlorobenzoate with N-chlorosuccinimide. The product wasisolated as a solid, m.p. 50°-52° C. The product was characterized by IRand ¹ H NMR spectroscopy and combustion analysis.

EXAMPLE 76 Preparation of methyl 3-amino-2-bromo-4-methylbenzoate

A mixture of 16.5 g (100 mmol) of methyl 3-amino-4-methylbenzoate and300 ml of CCl₄ was treated with 18.6 g (105 mmol) of N-bromosuccinimideand stirred at ambient temperature for 4 hours. The reaction mixture wasfiltered, and the filtrate was evaporated at reduced pressure to affordan amber oil. To remove material resulting from bromination at the6-position, the crude product was taken up in 100 ml of hexane and 60 mlof ether and treated with 3.96 g (50.0 mmol) of pyridine and 3.06 g(30.0 mmol) of acetic anhydride. After stirring for 3 hours at 25° C.,the precipitate was removed by filtration. The filtrate was evaporatedat reduced pressure to yield an amber oil. The crude product waspurified by HPLC to afford 14.5 g (59%) of the desired product as anamber oil. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₉ H₁₀ BrNO₂ : C, 44.29; H, 4.13; N, 5.74;Found: C, 44.14; H, 3.96; N, 5.72.

EXAMPLE 77 Preparation of methyl 3-methyl-4-chloro-anthranilate

This material was prepared by esterification of the correspondinganthranilic acid with HCl in methanol. The product was isolated as asolid, m.p. 72°-74° C.

EXAMPLE 78 Preparation of 2,6-dichloro-3-trifluoromethyl aniline

This material was prepared by chlorination of 2-chloro-5-trifluoromethylaniline with N-chlorosuccinimide followed by chromatographicpurification. The product was isolated as a yellow oil which wascharacterized by IR and ¹ H NMR spectroscopy and combustion analysis.

EXAMPLE 79 Preparation of 4-bromo-2,3-dichloro-6-methyl aniline

This material was prepared from 4-bromo-5-chloro-2-methyl aniline bychlorination with N-chlorosuccinimide. The product was isolated as asolid, m.p. 66°-68° C. The product was characterized by IR and ¹ H NMRspectroscopy and combustion analysis.

EXAMPLE 80 Preparation of 2,3-dichloro-6-methyl aniline

A slurry of 6.50 g (25.5 mmol) of 2,3-dichloro-4-bromo-6-methyl anilineand 8.37 g (102 mmol) of sodium acetate in 120 ml of acetic acid-ethanol(1:1, v/v) was treated with 0.65 g of 5% palladium on carbon. Themixture was hydrogenated in a Parr hydrogenation apparatus at an initialpressure of 50 psi for 10 minutes. The reaction mixture was filtered,and the filtrate was concentrated by evaporation at reduced pressure.The residue was partitioned between ether and water, and the organiclayer was washed with 5% aqueous sodium hydroxide, dried and evaporatedat reduced pressure. The residue was purified by Kugelrohr distillationto afford 4.00 g (89%) of the desired product as a colorless oil, b.p.60°-70° C. (0.15 mm). IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₇ H₇ Cl₂ N: C, 47.76; H, 4.01; N, 7.95; Found:C, 48.11; H, 4.04; N, 8.19.

EXAMPLE 81 Preparation of 2-amino-3-chlorobenzyl alcohol

A solution of 28.9 g (155 mmol) of methyl 3-chloro-anthranilate in 100ml of ether was added dropwise to a stirred suspension of 7.67 g (202mmol) of lithium aluminum hydride in 400 ml of ether. After stirring for5 hours at room temperature, the grey mixture was treated sequentiallywith 7.7 ml of water, 7.7 ml of 15% sodium hydroxide and 23 ml of water.The reaction mixture was filtered, and the filtrate was evaporated atreduced pressure. The oily residue was dissolved in ether, andprecipitation of the product was induced by addition of hexane. Theproduct was collected by filtration to yield a tan solid in 67% yield,m.p. 56°-68° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₇ H₈ ClNO: C, 53.35; H, 5.12; N, 8.88; Found:C, 53.16; H, 4.84; N, 9.28.

EXAMPLE 82 Preparation of 2-chloro-6-methoxymethylaniline

A solution of 4.00 g (25.4 mmol) of 2-amino-3-chlorobenzyl alcohol in 30ml of dry THF was cooled to -78° C., treated with 16.7 ml (26.7 mmol) of1.60M n-butyllithium in hexane, warmed to 0°-5° C., treated with 3.61 g(25.4 mmol) of methyl iodide and heated at reflux for 5.5 hours. Thesolvent was removed by evaporation at reduced pressure. The residue waspartitioned between 175 ml of ether and water, and the organic phase wasseparated and dried (MgSO₄). The solvent was removed by evaporation atreduced pressure, and the residue was purified by HPLC eluting withETOAc (5:95, v/v) to afford 1.1 g of the desired product as a pale brownoil. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₈ H₁₀ ClNO: C, 56.00; H, 5.87; N, 8.16; Found:C, 56.25; H, 5.98; N, 8.28.

EXAMPLE 83 Preparation of 2-acetoxymethyl-6-chloro aniline

This material was prepared from 2-amino-3-chlorobenzyl alcohol andacetyl chloride by the general procedure outlined in Example 82. Theproduct was isolated as an amber oil and was characterized by IR and ¹ HNMR spectroscopy and combustion analysis.

EXAMPLE 84 Preparation of 2-benzyloxymethyl-6-chloro aniline

This material was prepared from 2-amino-3-chlorobenzyl alcohol andbenzyl bromide by the general procedure outlined in Example 82. Theproduct was purified by Kugelrohr distillation to yield an oil, bp118°-125° C. (0.1 mm). The product was characterized by IR and ¹ H NMRspectroscopy.

EXAMPLE 85 Preparation of N-v butoxycarbony-2-fluoro aniline

A solution of 2-fluoroaniline (30.0 g, 0.27 mol) and di-t-butylcarbonate(66.5 g, 0.30 mol) in 100 ml of THF was heated at reflux for 4 hours.The solvent was removed by evaporation at reduced pressure, and theresidue was partitioned between 1M aqueous citric acid and ethylacetate. The organic phase was washed with saturated aqueous NaCl. Thesolvent was removed to afford the desired product with was used withoutfurther purification. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₁₁ H₁₄ FNO₂ : C, 62.55; H, 6.68; N, 6.63;Found: C, 62.45; H, 6.39; N, 6.21.

EXAMPLE 86 Preparation of 2-fluoro-6-methylaniline

A solution of 8.15 g (38.5 mmol) of N-t-butoxycarbonyl-2-fluoroanilinein 30 ml of dry THF was cooled to -70° C., and 46.3 ml (93 mmol) of 2.0Mt-butyllithium in pentane was added dropwise at a rate sufficient tomaintain the temperature below -65° C. When the addition was completethe reaction mixture was stirred at -70° C. for 15 minutes, warmed to-20° C. and stirred for 2.5 hours. A solution of 6.8 g (30 mmol) ofmethyl iodide in THF was added and the reaction was allowed to warm toroom temperature. The reaction mixture was partitioned between ether andwater, and the organic layer was washed with saturated aqueous NaCl anddried (MgSO₄). Evaporation at reduced pressure gave a yellow solid whichwas added to 25 ml of 3N HCl and heated at reflux for 3 hours. Aftercooling to room the pH of the solution was adjusted to pH 7, and thesolution was extracted twice with methylene chloride. The combinedorganic phases were washed with water and dried (MgSO₄). Evaporation atreduced pressure gave a yellow oil which was Kugelrohr distilled toyield 3.8 g (80%) of the desired product as a liquid, bp 91°-93° C. (0.1mm). IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₇ H₈ FN: C, 67.20; H, 6.45; N, 11.20; Found:C, 67.61; H, 6.09; N, 11.53.

EXAMPLE 87 Preparation of 2-fluoro-6-methylthioaniline

This material was prepared for N-t-butoxycarbonyl-2-fluoroaniline anddimethyl disulfide following the general procedure outlined in Example86. IR and ¹ H NMR spectra of the product were consistent with theassigned structure.

EXAMPLE 88 Preparation of2-(2-chloro-4-trifluoromethylphenoxy)nitrobenzene

A mixture of 29.4 g (0.200 mol) of 2-fluoro nitrobenzene, 41.0 g (0.200mol) of 2-chloro-4-trifluoromethylphenol and 30.0 g (0.220 mol) of K₂CO₃ in 150 ml of DMSO was heated at 100° C. for 6 hours. The reactionmixture was poured over ice and extracted with ether. The organic phasewas washed with water and saturated aqueous NaCl and dried (MgSO₄). Thesolvent was removed by evaporation at reduced pressure to yield 56.1 g(88%) of the desired product as a yellow oil. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₇ ClF₃ NO₃ : C, 49.15; H, 2.22; N, 4.41;Found: C, 49.47; H, 2.07; N, 4.13.

EXAMPLE 89 Preparation of 2-(2-chloro-4-trifluoromethylphenoxy)aniline

Raney Nickel (4.0 g) was washed with water and added to 250 ml ofethanol. To this mixture under a nitrogen blanket was added 56 g (0.18mol) of 2-(2-chloro-4-trifluoromethyl)phenoxy nitrobenzene. This mixturewas hydrogenated in a Parr hydrogenation apparatus at an initialpressure of 50 psi. The catalyst was removed by filtration throughcelite and the filtrate was evaporated at reduced pressure to yeild 49.9g (100%) of the desired product as an amber oil. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₉ ClF₃ NO: C, 54.27; H, 3.15; N, 4.87;Found: C, 54.72; H, 3.01; N, 4.61.

EXAMPLE 90 Preparation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)nitrobenzene

This material was prepared in 63% yield from3-chloro-2-fluoro-5-trifluoromethylpyridine and 2-nitrophenol followingthe general procedure outlined in Example 88. The product was isolatedas an amber oil which was characterized by IR and ¹ H NMR spectroscopy.

EXAMPLE 91 Preparation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline

This material was prepared in 61% yield by hydrogenation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)nitrobenzene following thegeneral procedure outlined in Example 89. The crude product wasrecrystallized from hexane to yield the desired product as whiteneedles, m.p. 133°-135° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis: Calculated for C₁₂ H₈ ClF₃ N₂ O: C, 49.94; H, 2.79; N, 30.50;Found: C, 49.93; H, 2.91; N, 30.27.

EXAMPLE 92 Preparation of 2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoronitrobenzene

This material was prepared in 47% yeild from 2,6-difluoronitrobenzeneand 2-chloro-4-trifluoromethylphenol following the general procedureoutlined in Example 88. The product was isolated as an oil which wascharacterized by IR and ¹ H NMR spectroscopy.

EXAMPLE 93 Preparation of2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoroaniline

This material was prepared in 72% yield by hydrogenation of2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoro nitrobenzene followingthe general procedure outlined in Example 89. The crude product wasKugelrohr distilled to yield the desired product as a liquid, bp.102°-103° C. (10 mm). IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₁₃ H₈ ClF₄ NO: C, 51.09; H, 2.64; H, 9.17;Found: C, 51.34; H, 2.41; H, 9.16.

The compounds prepared employing the above general procedures and theappropriate starting materials are tabulated in the following Tables Ithrough XLV.

    TABLE I      ##STR41##       Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Melting Point     Elemental Analysis              Analysis C H N Cl S  1 H H H H H 195°-198° C.     Calcd. for C.sub.13 H.sub.13 N.sub.5 O.sub.2 S: 51.48 4.32 23.08     Found: 50.86 4.26 23.12  2 CH.sub.3 H H H H 222°-224° C.     Calcd. for C.sub.14 H.sub.15 N.sub.5 O.sub.2 S: 52.99 4.76 22.06     Found: 52.75 4.79 22.25  3 OH H H H H >150° C. (decomp.) Calcd.     for C.sub.13 H.sub.13 N.sub.5 O.sub.3 S: 48.90 4.10 21.92        Found:     48.45 4.15 21.77  4 OCH.sub.3 H H H H 208°-210.5° C.     Calcd. for C.sub.14 H.sub.15 N.sub.5 O.sub.3 S: 50.44 4.54 21.00     Found: 50.17 4.54 21.12  5 NHCH.sub.3 H H H H 227°-228° C.     Calcd. for C.sub.14 H.sub.16 N.sub.6 O.sub.2 S: 50.59 4.85 25.28     Found: 49.70 4.87 25.12  6 I H H H H 189°-192° C. Calcd.     for C.sub.13 H.sub.12 IN.sub.5 O.sub.2 S: 36.38 2.82 16.31        Found:     36.61 2.81 16.15  7 Cl H H H H   188°-189.5° C. Calcd. for     C.sub.13 H.sub.12 ClN.sub.5 O.sub.2 S: 46.23 3.58 20.73 10.50 9.49      Found: 46.09 3.58 20.89 10.34 9.37  8 F H H H H 189°-190°     C. Calcd. for C.sub.13 H.sub.12 FN.sub.5 O.sub.2 S: 48.59 3.76 21.79     9.98        Found: 48.79 3.74 21.88  9.86      9 SCH.sub.3 H H H H 142°-144° C. Calcd. for C.sub.14     H.sub.15 N.sub.5 O.sub.2 S.sub.2 : 48.13 4.33 20.04        Found: 47.99     4.28 20.40 10 COOCH.sub.3 H H H H 169.5°-170.5° C. Calcd.     for C.sub.15 H.sub.15 N.sub.5 O.sub.4 S: 49.86 4.18 19.38  8.87     Found: 49.68 4.13 19.35  8.69 11 COOH H H H H 247°-248° C.     Calcd. for C.sub.14 H.sub.13 N.sub.5 O.sub.4 S: 48.41 3.77 20.16  9.23          Found: 47.87 3.66 20.27  8.87 12 NO.sub.2 H H H H 140° C.     Calcd. for C.sub.13 H.sub.12 N.sub.6 O.sub.4 S: 44.83 3.47 24.13  9.21          Found: 44.91 3.48 24.11  9.11 13 CF.sub.3 H H H H 198.5-200.5.degree     . C. Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5 O.sub.2 S: 45.28 3.26     18.86  8.63        Found: 45.39 3.16 18.74  8.87 14 CN H H H H 237.5-239.     degree. C. Exact mass calcd for C.sub.14 H.sub.12 N.sub.6 O.sub.2 S:     328.0742        Found: 328.0748        Analysis C H N Cl S 15 SO.sub.2     NMe.sub.2 H H H H  91° C. Calcd. for C.sub.15 H.sub.18 N.sub.6     O.sub.4 S.sub.2 : 43.89 4.42 20.47  15.62        Found: 44.25 4.37 20.21      15.23 16 SO.sub.2 N(Me)Et H H H H  80° C. Calcd. for C.sub.16     H.sub.20 N.sub.6 O.sub.4 S.sub.2 : 45.27 4.75 19.80 15.11        Found:     45.07 4.64 19.60  14.77 17 H Cl H H H   231°-232.5° C.     Exact mass calcd. for C.sub.13 H.sub.12 ClN.sub.5 O.sub.2 S: 337.0400         Found: 337.0415 18 H H Cl H H 237°-239° C. Exact mass     calcd. for C.sub.13 H.sub.12 ClN.sub.5 O.sub.2 S: 337.0400        Found:     337.0411        Analysis C H N Cl S 19 Cl Cl H H H 214.5°-216.5.de     gree. C. Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2 S: 41.95     2.98 18.81 19.05 8.61        Found: 42.02 3.03 18.99 18.24 8.30 20 Cl H     Cl H H   176°-177.5° C. Calcd. for C.sub.13 H.sub.11     Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found:     42.24 2.94 18.90 18.83 8.82 21 Cl H H Cl H 250°-253° C.     Exact mass calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2 S:     371.0010        Found: 370.9997        Analysis C H N Cl S 22 Cl H H H     Cl 260.5°-262.5° C. Calcd. for C.sub.13 H.sub.11 Cl.sub.2     N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found: 42.12 2.94     19.01 18.89 8.57 23 H Cl Cl H H 240°-242° C. Calcd. for     C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05     8.61        Found: 42.32 2.87 18.82 18.65 8.42 24 H Cl H Cl H 273.5.degre     e.-275.5° C. Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5     O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found: 42.30 2.89 18.42     18.85 8.49 25 F H H H F 229.5°-231° C. Exact mass calcd.     for C.sub.13 H.sub.11 F.sub.2 N.sub.5 O.sub.2 S: 339.0630        Found:     339.0602        Analysis C H N Cl S 26 COOMe H H H F 181.5°-183.5.     degree. C. Calcd. for C.sub.15 H.sub.14 FN.sub.5 O.sub.4 S: 47.49 3.72     18.46  8.45        Found: 47.65 3.60 18.19  8.35 27 COOH H H H F     228.5°-230° C.   Calcd. for C.sub.14 H.sub.12 FN.sub.5     O.sub.4 S: 46.03 3.31 19.17  8.78        Found: 45.56 3.26 19.05  8.50     28 SO.sub.2 NMe.sub.2 H H CF.sub.3 H 174.5°-176.5° C.     Calcd. for C.sub.16 H.sub.17 F.sub.3 N.sub.6 O.sub.4 S.sub. 2 : 40.16     3.58 17.56  13.40        Found: 40.16 3.49 17.39  13.17 29 F H F H H     223°-224.5° C. Calcd. for C.sub.13 H.sub.11 F.sub.2     N.sub.5 O.sub.2 S: 46.02 3.27 20.63        Found: 46.19 3.37 20.59 30 Cl     H F H H 203°-205° C. Calcd. for C.sub.13 H.sub.11      ClFN.sub.5 O.sub.2 S: 43.89 3.12 19.68        Found: 44.02 3.12 19.89     31 Cl H H H CH.sub.3   230°-231.5° C. Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S: 47.82 3.98 19.07       (decomp.) Found:     47.87 4.06 19.66 32 CH.sub.3 H H H CH.sub.3 263°-266° C.     Calcd. for C.sub.15 H.sub.17 N.sub.5 O.sub.2 S: 54.31 5.23 21.23     (decomp.) Found: 53.59 5.07 20.65 33 CH.sub.2 CH.sub.3 H H H CH.sub.2     CH.sub.3   248°-249.5°  C. Calcd. for C.sub.17 H.sub.21     N.sub.5 O.sub.2 S: 56.83 5.84 19.48       (decomp.) Found: 57.06 5.98     19.40 34 CF.sub.3 H Cl H H 189°-193° C. Calcd. for     C.sub.14 H.sub.11 ClF.sub.3 N.sub.5 O.sub.2 S: 41.41 2.71 17.25     (decomp.) Found: 41.78 2.73 17.23 35 Cl H Cl H Cl >200° C.     (decomp.) Calcd. for C.sub.13 H.sub.10 Cl.sub.3 N.sub.5 O.sub.2 S: 38.40     2.48 17.22        Found: 38.36 2.48 17.14 36 COO.sub.-iPr H H H H     130°-132° C. Calcd. for C.sub.17 H.sub.19 N.sub.5 O.sub.4     S: 52.43 4.92 17.98        Found: 51.83 4.77 17.70 37 CONH.sub.2 H H H H     258°-260° C. Calcd. for C.sub.14 H.sub.14 N.sub.6 O.sub.3     S: 48.55 4.07 24.26        Found: 48.58 4.00 24.01 38 Br H H H Br     285°-287°  C. Calcd. for C.sub.13 H.sub.11 Br.sub.2     N.sub.5 O.sub.2 S: 33.86 2.40 15.18        Found: 33.92 2.42 15.41 39 Br     H H H Cl >230° C. (decomp.) Calcd. for C.sub.13 H.sub.11      BrClN.sub.5 O.sub.2 S: 37.47 2.66 16.80        Found: 37.50 2.64 16.87     40 Br H Cl H H 177°-179° C. Calcd. for C.sub.13 H.sub.11     BrClN.sub.5 O.sub.2 S: 37.47 2.66 16.80        Found: 37.45 2.67 16.64     41 Br H H H H 188°-190° C. Calcd. for C.sub.13 H.sub.12     BrN.sub.5 O.sub.2 S: 40.85 3.16 18.32        Found: 41.09 3.12 18.19 42     CONMe.sub.2 H H H H 193°-194° C. Calcd. for C.sub.16     H.sub.18 N.sub.6 O.sub.3 S: 51.33 4.85 22.44        Found: 51.08 4.65     22.12 43 CONMe.sub.2 H Cl H H 194°-195° C. Calcd. for     C.sub.16 H.sub.17 ClN.sub.6 O.sub.3 S: 47.00 4.19 20.55        Found:     47.16 4.07 20.50 44 Cl H F H Cl 271°-273° C. Calcd. for     C.sub.13 H.sub.10 Cl.sub.2 FN.sub.5 O.sub.2 S: 40.02 2.58 17.94     (decomp.) Found: 40.13 2.65 18.04 45 SO.sub.2      Me H H H H 181°-183° C. Calcd. for C.sub.14 H.sub.15     N.sub.5 O.sub.4 S.sub.2 : 44.09 3.96 18.35        Found: 43.64 3.84     18.16 46 Cl Me H H Cl 280° C. (decomp.) Calcd. for C.sub.14     H.sub.13 Cl.sub.2 N.sub.5 O.sub.2 S: 43.54 3.39 18.13        Found:     43.45 3.37 18.15 47 Cl H Me H Cl 245°-248° C. Calcd. for     C.sub.14 H.sub.13 Cl.sub.2 N.sub.5 O.sub.2 S: 43.54 3.39 18.13     Found: 43.57 3.37 18.21 48 Cl H Me H H 229°-231° C. Calcd.     for C.sub.14 H.sub.14 ClN.sub.5 O.sub.2 S: 48.00 4.01 19.90     Found: 48.01 3.97 20.05 49 NO.sub.2 H H H CH.sub.3 244°-246.degree     . C. Exact mass calcd. for C.sub.14 H.sub.14 N.sub.6 O.sub.4 S: 362.0799            Found: 362.0807        Analysis C H N Cl S 50 COOMe H H H     CH.sub.3   190°-192.5° C. Calcd. for C.sub.16 H.sub.17     N.sub.5 O.sub.4 S: 51.19 4.57 18.65        Found: 51.22 4.58 18.46 51     COO.sub.-i-Pr H H H F 167°-168° C. Calcd. for C.sub.17     H.sub.18 FN.sub.5 O.sub.4 S: 50.12 4.45 17.18        Found: 50.09 4.39     17.28 52 Cl H H CF.sub.3 H 221.5°-224° C.   Calcd. for     C.sub.14 H.sub.10 ClF.sub. 3 N.sub.5 O.sub.2 S: 41.43 2.71 17.24     Found: 41.73 2.74 17.08 53 I H H H Cl >258° C. (decomp.) Calcd.     for C.sub.13 H.sub.11 ClIN.sub.5 O.sub.2 S: 33.68 2.39 15.10     Found: 33.66 2.38 15.03  54* Cl H H H F   223°-225.5° C.     Calcd. for C.sub.13 H.sub.11 ClFN.sub.5 O.sub.2 S: 43.89 3.12 19.68      (decomp.) Found: 43.20 2.89 19.41 55 SCF.sub.3 H H H H 175-178°     C. Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5 O.sub.2 S.sub.2 41.68     2.97 17.35        Found: 40.84 2.95 16.61 56 COO.sub.-t-Bu H H H F     151-153° C. Calcd. for C.sub.18 H.sub.20 FN.sub.5 O.sub.4 S:     51.30 4.78 16.61       (decomp.) Found: 50.90 4.69 16.49 57 SO.sub.2     CF.sub.3 H H H H 68-70° C. Calcd. for C.sub.14 H.sub.12 F.sub.3     N.sub.5 O.sub.4 S.sub.2 : 38.62 2.75 16.09        Found: 39.10 2.71     15.87 58 Br H H H CH.sub.3 225-228° C. Calcd. for C.sub.14     H.sub.14 BrN.sub.5 O.sub.2 S: 42.44 3.56 17.67        Found: 42.56 3.55     17.66 59 SCF.sub.2 CF.sub.2 H H H H H 162.5-164° C.   Calcd. for     C.sub.15 H.sub.13 F.sub.4 N.sub.5 O.sub.2 S.sub.2 : 41.38 3.01 16.08     14.73        Found: 41.54 2.88 16.06  14.57 60 SOCF.sub.2 CF.sub.2 H H H     H H 223-224° C. Calcd. for C.sub.15 H.sub.13 F.sub.4 N.sub.5     O.sub.3 S.sub.2 : 39.91 2.90 15.51  14.21        Found: 39.88 2.83 15.37      14.15 61 CONH.sub.2 H H H CH.sub.3 231-232° C. Calcd. for     C.sub.15 H.sub.16 N.sub.6 O.sub.3 S.H.sub.2 O: 47.61 4.80 22.20     Found: 47.74 4.71 22.04 62 CONMe.sub.2 H H H CH.sub.3 225-257° C.     Calcd. for C.sub.17 H.sub.16 N.sub.6 O.sub.3 S: 52.57 5.19 21.63     Found: 52.15 5.15 21.39 63 Cl H H H Ph 256.260° C. Calcd. for     C.sub.19 H.sub.16 ClN.sub.5 O.sub.2 S: 55.14 3.90 16.92       (decomp.)     Found: 54.68 3.89 16.96 64 COO.sub.-i-Pr H H H CH.sub.3 178-179°     C. Calcd. for C.sub.18 H.sub.21 N.sub.5 O.sub.4 S: 53.59 5.25 17.35       Found: 53.32 5.18 17.15 65 CH.sub.3 Cl H H CH.sub.3 279-282° C.     Calcd. for C.sub.15 H.sub.16 C'N.sub.5 O.sub.2 S: 49.25 4.41 19.14     (decomp.) Found: 49.05 4.38 19.00 66 SCH.sub.2 CHCH.sub.2 H H H H     113-114° C. Calcd. for C.sub.16 H.sub.17 N.sub.5 O.sub.2 S.sub.2     : 51.17 4.56 18.65        Found: 51.29 4.63 18.94 67 SCH.sub.2 CH.sub.2     CH.sub.3 H H H H 124° (decomp.) Calcd. for C.sub.16 H.sub.19     N.sub.5 O.sub.2 S.sub.2 : 50.90 5.07 18.55        Found: 50.41 4.76     18.79 68 CH.sub.3 Cl H H H 223-225° C. Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S: 47.79 4.01 19.91        Found: 47.52 4.31     19.84 69 SCH.sub.3 H H H Cl 171-172° C. Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S.sub.2 : 43.80 3.68 18.24        Found:     44.00 3.74 17.96 70 SCH.sub.3 H H H CH.sub.3 200-202° C. Calcd.     for C.sub.15 H.sub.17 N.sub.5 O.sub.2 S.sub.2 : 49.56 4.71 19.27     Found: 49.78 4.49 18.68 71 CHNOH H H H OCH.sub.3 244-246° C.     Calcd. for C.sub.15 H.sub.16 N.sub.6 O.sub.4 S: 47.86 4.29 22.33     Found: 47.47 4.03 23.36 72 CO.sub.2 CH.sub.2 CH.sub.2 OEt H H H CH.sub.3     78-80° C. Calcd. for C.sub.19 H.sub.23 N.sub.5 O.sub.5 S: 52.65     5.35 16.16        Found: 51.68 5.11 16.37 73 CO.sub.2 CH.sub.2 CH.sub.2     NMe.sub.2 H H H CH.sub.3 207-208° C. Calcd. for C.sub.19 H.sub.24     N.sub.6 O.sub.4 S: 52.76 5.59 19.43        Found: 52.06 5.48 19.18 74 Cl     Cl H H CH.sub.3 287-289° C. Calcd. for C.sub.14 H.sub.13 Cl.sub.2     N.sub.5 O.sub.2 S: 43.54 3.39 18.13       (decomp.) Found: 43.74 3.46     18.48 75 COOPh H H H CH.sub.3 159.5-160.5° C. Calcd. for C.sub.21     H.sub.19 N.sub.5 O.sub.4 S: 57.66 4.38 16.01        Found: 57.17 4.46     15.74 76 CO.sub.2 CH.sub.2 CHCH.sub.2 H H H CH.sub.3   158-158.5°     C. Calcd. for C.sub.18 H.sub.19 N.sub.5 O.sub.4 S: 53.86 4.77 17.44       Found: 53.47 4.63 17.54 77 CO.sub.2 CH.sub.2      N H H H CH.sub.3 165.5-166° C.   Calcd. for C.sub.21 H.sub. 20     N.sub.6 O.sub.4 S: 55.74 4.46 18.57        Found: 55.82 4.43 18.32 78     CO.sub.2 NC(CH.sub.3).sub.2 H H H CH.sub.3 91-94° C. Calcd. for     C.sub.18 H.sub.20 N.sub.6 O.sub.4 S: 51.91 4.84 20.18        Found:     51.51 4.68 19.70 79 CHNOCH.sub.3 H H H OCH.sub.3 227-229° C.     Calcd. for C.sub.16 H.sub.18 N.sub.6 O.sub.4 S: 49.22 4.65 21.53     Found: 49.00 4.63 21.24 80 S.sub.-t-Bu H H H H 144-146° C. Calcd.     for C.sub.17 H.sub.21 N.sub.5 O.sub.2 S.sub.2 : 52.15 5.41 17.89     Found: 52.31 5.34 17.92 81 Cl H H COOMe H 175-177° C. Calcd. for     C.sub.15 H.sub.14 ClN.sub.5 O.sub.4 S: 45.52 3.57 17.69        Found:     45.42 3.45 17.66 82 Cl COOMe H H Cl 217-221° C. Calcd. for     C.sub.15 H.sub.13 Cl.sub.2 N.sub.5 O.sub. 4 S: 41.87 3.05 16.27     (decomp.) Found: 41.96 3.10 16.22 83 Cl CF.sub.3 H H Cl 286-290°     C. Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3 N.sub.5 O.sub.2 S:     38.20 2.29 15.90       (decomp.) Found: 38.36 2.29 16.63 84 Cl H H     CO.sub.2.sub.-i-Pr H 182-185° C. Calcd. for C.sub.17 H.sub.18     ClN.sub.5 O.sub.4 S: 48.17 4.28 16.52        Found: 48.31 4.17 16.51 85     NO.sub.2 H H CH.sub.3 CH.sub.3 254-257° C. Calcd. for C.sub.15     H.sub.16 N.sub.6 O.sub.4 S: 47.87 4.29 22.32       (decomp.) Found:     47.52 4.01 22.47 86 Br COOMe H H CH.sub.3 229-231° C. Calcd. for     C.sub.16 H.sub.16 BrN.sub.5 O.sub.4 S: 42.30 3.55 15.41        Found:     42.29 3.45 15.68 87 Br COO.sub.-i-Pr H H CH.sub.3 208-211° C.     Calcd. for C.sub.18 H.sub.20 BrN.sub.5 O.sub.4 S: 44.82 4.18 14.51      Found: 45.09 4.11 14.39 88 Br COO.sub.-t-Bu H H CH.sub.3 181-183°      C. Calcd. for C.sub.19 H.sub.22 BrN.sub.5 O.sub.4 S: 45.98 4.47 14.10         (decomp.) Found: 45.61 4.17 13.84 89 COMe H H H H 166-168° C.     Calcd. for C.sub.15 H.sub.15 N.sub.5 O.sub.3 S: 52.16 4.38 20.28     Found: 52.07 4.19 20.37 90 F F H F F 148-149° C. Calcd. for     C.sub.13 H.sub.9 F.sub.4 N.sub.5 O.sub.2 S: 41.60 2.42 18.66     (decomp.) Found: 42.25 2.50 18.52 91 CH.sub.2 OCH.sub.3 H H H Cl     201-202° C. Calcd. for C.sub.15 H.sub.16 ClN.sub.5 O.sub.3 S:     47.19 4.22 18.33        Found: 47.07 4.16 18.87 92 CH.sub.2 OCHPh H H H     Cl 169-171° C. Calcd. for C.sub.21 H.sub.20 ClN.sub.5 O.sub.3 S:     55.08 4.40 15.29        Found: 54.99 4.38 15.30 93 CH.sub.2 OH H H H Cl     208-209° C. Calcd. for C.sub.14 H.sub.14 ClN.sub.5 O.sub.3     S.H.sub.2 O: 43.60 4.18 18.14        Found: 43.50 3.75 18.43 94 CH.sub.2     OAc H H H Cl 214-217° C. Calcd. for C.sub.16 H.sub.16 ClN.sub.5     O.sub.4 S: 46.89 3.94 17.08        Found: 46.60 3.80 17.73 95 COPh H H H     H 169-170° C. Calcd. for C.sub.20 H.sub.17 N.sub.5 O.sub.3 S:     58.95 4.21 17.19        Found: 58.67 4.14 17.51 96 SO.sub.2 Ph H H H H     152-154° C. Calcd. for C.sub.19 H.sub.17 N.sub.5 O.sub.4 S.sub.2     : 51.46 3.86 15.79        Found: 51.31 3.81 15.81      97     ##STR42##      H H H H 176-177° C. Calcd. for C.sub.20 H.sub.15 ClF.sub.3     N.sub.5 O.sub.3 S:Found: 48.2448.11 3.033.09 14.0614.49      98     ##STR43##      H H H F 211-213° C. Calcd. for C.sub.20 H.sub.14 ClF.sub.4     N.sub.5 O.sub.3 S:Found: 46.5646.02 2.742.74 13.5713.40      99     ##STR44##      H H H H 178-180° C. Calcd. for C.sub.19 H.sub.14 ClF.sub.3     N.sub.6 O.sub.3 SFound: 45.7445.66 2.842.81 16.8517.02  100  Cl H H COOH     H 276-278° C. Calcd. for C.sub.14 H.sub.12 ClN.sub.5 O.sub.4 S:     44.04 3.17 18.34        Found: 44.06 3.24 18.37 101  Br COOH H H     CH.sub.3 290° C. (decomp.) Calcd. for C.sub.15 H.sub.14 BrN.sub.5     O.sub.4 S: 40.92 3.21 15.90        Found: 40.51 3.11 16.01 102  CO.sub.2     Me H H CO.sub.2 Me H 191-194° C. Calcd. for C.sub.17 H.sub.17     N.sub.5 O.sub.6 S: 48.68 4.09 16.70        Found: 48.47 4.01 16.32 103     COOH H H H CH.sub.3 268-271° C. Calcd. for C.sub.15 H.sub.15     N.sub.5 O.sub.4 S.1/2H.sub.2 O: 48.64 4.35 18.90        Found: 48.88     4.00 19.20 104  CF.sub.3 H H H OCH.sub.3 246-249° C. Calcd. for     C.sub.15 H.sub.14 F.sub.3 N.sub.5 O.sub.3 S: 44.91 3.49 17.47     Found: 44.77 3.61 17.94     *This compound contains 15% where R.sup.1 = R.sup.3 = Cl and R.sup.5 = F.

                                      TABLE II                                    __________________________________________________________________________     ##STR45##                                                                                                 Elemental Analysis                               Compound                                                                            R.sup.1 R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                            __________________________________________________________________________    105   NO.sub.2                                                                              H H H H 110°-112° C.                                                           Calcd. for c.sub.15 H.sub.14 N.sub.6 O.sub.4                                  S:            48.11                                                                            3.73                                                                             22.43                                              (decomp.)                                                                            Found:        46.96                                                                            3.54                                                                             21.62                        106   CF.sub.3                                                                              H H H H ˜200° C.                                                                Calcd. for C.sub.16 H.sub.14 F.sub.3 N.sub.5                                  O.sub.2 S:    48.35                                                                            3.52                                                                             17.61                                                     Found:        48.08                                                                            3.40                                                                             17.40                        107    SO.sub.2 NMe.sub.2                                                                   H H H H 188°-189° C.                                                           Calcd. for C.sub.17 H.sub.20 N.sub.6 O.sub.4                                  S.sub.2 :     46.78                                                                            4.58                                                                             19.24                                              (decomp.)                                                                            Found:        46.04                                                                            4.85                                                                             18.90                        108   Cl      H H H H 264°-266° C.                                                           Calcd. for C.sub.15 H.sub.13 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          45.24                                                                            3.29                                                                             17.58                                                     Found:        45.47                                                                            3.18                                                                             17.41                        109   COOMe   H H H H 180°-182° C.                                                           Calcd. for C.sub.17 H.sub.17 N.sub.5 O.sub.4                                  S:            52.71                                                                            4.42                                                                             18.07                                              (decomp.)                                                                            Found:        52.19                                                                            4.28                                                                             18.12                        110   COO .sub.-i-Pr                                                                        H H H H 170°-172° C.                                                           Calcd. for C.sub.19 H.sub.21 N.sub.5 O.sub.4                                  S:            54.93                                                                            5.10                                                                             16.85                                                     Found:        54.82                                                                            5.01                                                                             16.59                        __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________     ##STR46##                                                                                             Elemental Analysis                                   Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N  S  Cl                         __________________________________________________________________________    111   Cl H H H Cl 296-298° C.                                                                   Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:    43.53                                                                            3.39                                                                             18.13                                                                            8.30                                                                             18.36                                               Found:        44.07                                                                            3.42                                                                             18.16                                                                            7.89                                                                             17.73                      112   CF.sub.3                                                                         H H H H  197-199° C.                                                                   Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5                                  O.sub.2 S:    46.75                                                                            3.66                                                                             18.17                                                                            8.32                                                   Found:        46.54                                                                            3.52                                                                             18.30                                                                            8.59                          113   Cl H H H CH.sub.3                                                                         306-309° C.                                                                   Calcd. for C.sub.15 H.sub.16 ClN.sub.5 O.sub.2                                S:            49.25                                                                            4.41                                                                             19.14                                                                            8.76                                                                             9.69                                                Found:        48.70                                                                            4.29                                                                             19.23                                                                            8.82                                                                             9.57                       __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________     ##STR47##                                                                                                    Elemental Analysis                            Compound                                                                            R.sup.1                                                                              R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                         __________________________________________________________________________    114   Cl     H   H  H Cl 246-248° C.                                                                   Calcd. for C.sub.11 H.sub.6 Cl.sub.3                                          N.sub.5 O.sub.2 S:                                                                          34.89                                                                            1.60                                                                             18.50                                                     Found:        35.02                                                                            1.65                                                                             18.09                     115   SMe    H   H  H H  159-162° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S.sub.2 :                                                                           40.50                                                                            2.81                                                                             19.60                                                     Found:        40.39                                                                            2.95                                                                             19.90                     116   F      H   H  H Cl 254-257° C.                                                                   Calcd. for C.sub.11 H.sub.6 Cl.sub.2                                          FN.sub.5 O.sub.2 S:                                                                         36.48                                                                            1.67                                                                             19.34                                                     Found:        37.21                                                                            1.91                                                                             18.74                     117   F      H   H  H F  224-226° C.                                                                   Calcd. for C.sub.11 H.sub.6 ClF.sub.2                                         N.sub.5 O.sub.2 S:                                                                          38.21                                                                            1.75                                                                             20.26                                                     Found:        38.32                                                                            1.44                                                                             20.18                     118   CF.sub.3                                                                             H   H  H H  179-180° C.                                                                   Calcd. for C.sub.12 H.sub.7 ClF.sub.3                                         N.sub.5 O.sub.2 S:                                                                          38.15                                                                            1.87                                                                             18.54                                                     Found:        38.19                                                                            1.59                                                                             18.00                     119   Cl     H   H  H CH.sub.3                                                                         223-226° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          40.23                                                                            2.53                                                                             19.55                                                     Found:        40.44                                                                            2.06                                                                             19.27                     120   H      H   H  H H  234° C.                                                                       Calcd. for C.sub.11 H.sub.8 ClN.sub.5                                         O.sub.2 S:    42.65                                                                            2.60                                                                             22.61                                                     Found:        41.67                                                                            2.56                                                                             22.01                     121   Cl     H   H  H H  188-189° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2                                          N.sub.5 O.sub. 2 S:                                                                         38.39                                                                            2.05                                                                             20.35                                                     Found:        38.26                                                                            1.84                                                                             19.98                     122   COOMe  H   H  H H  187-188° C.                                                                   Calcd. for C.sub.13 H.sub.10 ClN.sub.5                                        O.sub.4 S:    42.46                                                                            2.74                                                                             19.04                                                     Found:        42.54                                                                            2.79                                                                             19.13                     123   SO.sub.2 NMe.sub.2                                                                   H   H  H H  164-165° C.                                                                   Calcd. for C.sub.13 H.sub.13 ClN.sub.6                                        O.sub.4 S.sub.2 :                                                                           37.46                                                                            3.14                                                                             20.16                                                     Found:        37.42                                                                            3.21                                                                             20.25                     124   H      Br  H  H H  245-247° C.                                                                   Calcd. for C.sub.11 H.sub.7 BrClN.sub.5                                       O.sub.2 S:    34.00                                                                            1.82                                                                             18.02                                                     Found:        34.49                                                                            1.90                                                                             18.31                     125   H      H   CF.sub.3                                                                         H H  239-241° C.                                                                   Calcd. for C.sub.12 H.sub.7 F.sub.3                                           ClN.sub.5 O.sub.2 S:                                                                        38.16                                                                            1.87                                                                             18.54                                                     Found:        38.54                                                                            1.83                                                                             18.83                     126   CONMe.sub.2                                                                          H   H  H H  162-163° C.                                                                   Calcd. for C.sub.14 H.sub.13 ClN.sub.6                                        O.sub.3 S:    44.16                                                                            3.44                                                                             22.07                                                     Found:        44.57                                                                            3.47                                                                             22.43                     127   COO .sub.-iPr                                                                        H   H  H H  158-160° C.                                                                   Calcd. for C.sub.15 H.sub.14 ClN.sub.5                                        O.sub.4 S:    45.52                                                                            3.57                                                                             17.69                                                     Found:        45.54                                                                            3.49                                                                             17.93                     128   Cl     H   H  H Ph 243-245° C.                                                                   Calcd. for C.sub.17 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          48.58                                                                            2.64                                                                             16.66                                                     Found:        49.24                                                                            2.62                                                                             16.65                     129   CH.sub.3                                                                             H   H  H H  170-171° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S:    44.52                                                                            3.11                                                                             21.63                                                     Found:        44.66                                                                            3.04                                                                             21.96                     130   H      H    -n-Bu                                                                           H H  233-235° C.                                                                   Calcd. for C.sub.15 H.sub.16 ClN.sub.5                                        O.sub.2 S:    49.25                                                                            4.41                                                                             19.14                                                     Found:        49.10                                                                            4.30                                                                             19.30                     131   H      OCH.sub.3                                                                         H  H H  212-215° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.3 S:    42.42                                                                            2.97                                                                             20.61                                                     Found:        42.33                                                                            2.97                                                                             20.65                     132   SO.sub.2 N(Me)Et                                                                     H   H  H H  155-157° C.                                                                   Calcd. for C.sub.14 H.sub.15 ClN.sub.6                                        O.sub.4 S.sub.2 :                                                                           39.02                                                                            3.51                                                                             19.50                                                     Found:        39.17                                                                            3.47                                                                             19.54                     133   F      H   H  H H  171-172° C.                                                                   Calcd. for C.sub.11 H.sub.7 ClFN.sub.5                                        O.sub.2 S:    40.32                                                                            2.15                                                                             21.37                                                     Found:        41.00                                                                            2.18                                                                             21.55                     134   H      SCH.sub.3                                                                         H  H H  210-212° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S.sub.2 :                                                                           40.51                                                                            2.83                                                                             19.68                                                     Found:        39.29                                                                            2.77                                                                             19.70                     __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________     ##STR48##                                                                                                 Elemental Analysis                               Compound                                                                            R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                           Melting Point                                                                        Analysis     C  H  N                             __________________________________________________________________________    135   SCH.sub.3                                                                          H  H H H   162.5- 165° C.                                                                Calcd. for C.sub.12 H.sub.11 N.sub.5 O.sub.2                                  S.sub.2 :    44.85                                                                            3.43                                                                             21.78                                               (decomp.)                                                                            Found:       44.35                                                                            3.43                                                                             22.08                         136   CF.sub.3                                                                           H  H H H   168.5- 171° C.                                                                Calcd. for C.sub.12 H.sub.8 F.sub.3 N.sub.5                                   O.sub.2 S:   42.11                                                                            2.33                                                                             20.45                                               (decomp.)                                                                            Found:       41.93                                                                            2.28                                                                             19.99                         137   Cl   H  H H Cl  278-280° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2 N.sub.5                                  O.sub.2 S:   38.38                                                                            2.03                                                                             20.35                                                      Found:       38.28                                                                            1.70                                                                             20.75                         138   F    H  H H F   296-299° C.                                                                   Calcd. for C.sub.11 H.sub.7 F.sub.2 N.sub.5                                   O.sub.2 S:   42.46                                                                            2.25                                                                             22.52                                               (decomp.)                                                                            Found:       42.27                                                                            2.30                                                                             22.60                         139   Cl   CH.sub.3                                                                         H H Cl  252-255° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.2 S:   40.23                                                                            2.51                                                                             19.55                                               (decomp.)                                                                            Found:       40.00                                                                            2.65                                                                             19.75                         140   F    CH.sub.3                                                                         H H F   280-283° C.                                                                   Calcd. for C.sub.12 H.sub.9 F.sub.2 N.sub.5                                   O.sub.2 S:   44.32                                                                            2.77                                                                             21.55                                               (decomp.)                                                                            Found:       44.10                                                                            2.81                                                                             21.55                         141   CF.sub.3                                                                           H  H H OCH.sub.3                                                                         230-232° C.                                                                   Calcd. for C.sub.13 H.sub.10 F.sub.3 N.sub.5                                  O.sub.3 S:   41.80                                                                            2.68                                                                             18.78                                                      Found:       41.40                                                                            2.77                                                                             18.69                         __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________     ##STR49##                                                                    Compound                                                                            R.sup.1                                                                              R.sup.2                                                                           R.sup.3                                                                         R.sup.4                                                                          R.sup.5                                                                             Melting Point                                                                         Elemental Analysis                        __________________________________________________________________________                                        Analysis       C  H  N  S                 142   SCH.sub.3                                                                            H   H H  H     166°-169° C.                                                            Calcd. for C.sub.13 H.sub.13 N.sub.5                                          O.sub.2 S.sub.2 :                                                                            45.67                                                                            3.77                                                                             20.11                                                    Found:         47.34                                                                            3.90                                                                             19.86                143   Cl     H   H H  Cl    228.5°-230° C.                                                          Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                           40.24                                                                            2.51                                                                             19.54                                                    Found:         40.34                                                                            2.52                                                                             19.09                144   Cl     H   H H  CH.sub.3                                                                            211-215° C.                                                                    Calcd. for C.sub.13 H.sub.12 ClN.sub.5                                         O.sub.2 S:    46.19                                                                            3.55                                                                             20.72                                            (decomp.)                                                                             Found:         45.91                                                                            3.43                                                                             20.70                145   CF.sub.3                                                                             H   H H  H     144-145° C.                                                                    Calcd. for C.sub.13 H.sub.10 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                           43.67                                                                            2.79                                                                             19.59                                                    Found:         43.67                                                                            2.74                                                                             19.52                146   COOMe  H   H H  CH.sub.3                                                                            184-186° C.                                                                    Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.4 S:     49.84                                                                            4.15                                                                             19.38                                                    Found:         49.65                                                                            4.13                                                                             19.45                147   Cl     CH.sub.3                                                                          H H  Cl    140° C.                                                                        Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                           41.91                                                                            2.95                                                                             18.80                                            (decomp.)                                                                             Found:         41.92                                                                            2.83                                                                             18.45                148   Br     H   H H  CH.sub.3                                                                            106° C.                                                                        Calcd. for C.sub.13 H.sub.12 BrN.sub.5                                         O.sub.2 S:    40.83                                                                            3.14                                                                             18.32                                            (decomp.)                                                                             Found:         40.36                                                                            3.14                                                                             18.30                149   SOCF.sub.2 CF.sub.2 H                                                                H   H H  H     180° C.                                                                        Calcd. for C.sub.14 H.sub.11 F.sub.4                                          N.sub.5 O.sub.3 S.sub.2 :                                                                    38.40                                                                            2.52                                                                             16.03                                            (decomp.)                                                                             Found:         36.70                                                                            2.50                                                                             14.69                150   SCH.sub.3                                                                            H   H H  CH.sub.3                                                                            234° C.                                                                        Calcd. for C.sub.14 H.sub.15 N.sub.5                                          O.sub.2 S.sub.2 :                                                                            48.12                                                                            4.33                                                                             20.04                                            (decomp.)                                                                             Found:         47.89                                                                            4.17                                                                             20.31                151   NO.sub.2                                                                             H   H H  CH.sub.3                                                                            120° C.                                                                        Calcd. for C.sub.13 H.sub.12 N.sub.6                                          O.sub.4 S:     44.82                                                                            3.47                                                                             24.13                                            (decomp.)                                                                             Found:         45.94                                                                            3.30                                                                             23.75                152   Br     H   H H  Cl    230-235° C.                                                                    Calcd. for C.sub.12 H.sub.9 BrClN.sub.                                        5 O.sub.2 S:   35.79                                                                            2.25                                                                             17.39                                                    Found:         35.50                                                                            2.19                                                                             17.97                153   I      H   H H  Cl    210-215° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClIN.sub.5                                         O.sub.2 S:    32.05                                                                            2.02                                                                             15.58                                                    Found:         32.36                                                                            2.29                                                                             15.31                154   Cl     H   H H  Ph    233-234° C.                                                                    Calcd. for C.sub.18 H.sub.14 ClN.sub.5                                         O.sub.2 S:    54.07                                                                            3.53                                                                             17.52                                                                            8.02                                          (decomp.)                                                                             Found:         53.49                                                                            3.45                                                                             17.82                                                                            8.49              155   Cl     Cl  H H  CH.sub.3                                                                            256-259° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                           41.95                                                                            2.98                                                                             18.81                                                                            8.61                                          (decomp.)                                                                             Found:         42.00                                                                            2.96                                                                             18.75                                                                            8.63              156   COOCH.sub.3                                                                          H   H Cl CH.sub.3                                                                            75-80° C.                                                                      Calcd. for C.sub.15 H.sub.14 ClN.sub.5                                         O.sub.4 S:    45.52                                                                            3.57                                                                             17.69                                                                            8.10                                                  Found:         45.28                                                                            3.57                                                                             17.41                                                                            8.07              157   F      H   H H  F     245-247° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2                                           N.sub.5 O.sub.2 S:                                                                           44.30                                                                            2.79                                                                             21.53                                                    Found:         44.69                                                                            2.80                                                                             21.85                158   F      H   H H  Cl    243-248° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClFN.sub.5                                         O.sub.2 S:    42.17                                                                            2.65                                                                             20.49                                                    Found:         42.14                                                                            2.63                                                                             20.18                159   COOMe  H   H H  F     159-163° C.                                                                    Calcd. for C.sub.14 H.sub.12 FN.sub.5                                         O.sub.4 S:     46.03                                                                            3.31                                                                             19.16                                                    Found:         45.56                                                                            3.08                                                                             19.25                160   NO.sub. 2                                                                            H   H CH.sub.3                                                                         CH.sub.3                                                                            225-230° C.                                                                    Exact mass calcd for C.sub.14                                                 H.sub.14 N.sub.6 O.sub.4 S:                                                                    262.0799                                                     Found:           262.0802                                                     Analysis:      C  H  N  S                 161   F      H   H H  SCH.sub.3                                                                           190-192° C.                                                                    Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.2 S.sub.2 :                                                                            44.18                                                                            3.42                                                                             19.82                                                    Found:         44.02                                                                            3.41                                                                             19.51                162   F      H   H H  CH.sub.3                                                                            241° C.                                                                        Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.2 S:     48.59                                                                            3.76                                                                             21.80                                            (decomp.)                                                                             Found:         48.31                                                                            3.51                                                                             21.62                163   F      F   H F  F     209° C.                                                                        Calcd. for C.sub.12 H.sub.7 F.sub.4                                           N.sub.5 O.sub.2 S:                                                                           39.89                                                                            1.95                                                                             19.39                                            (decomp.)                                                                             Found:         38.41                                                                            2.21                                                                             19.04                164   CH.sub.2 OCH.sub.3                                                                   H   H H  Cl    186-191° C.                                                                    Calcd. for C.sub.14 H.sub.14 ClN.sub.5                                         O.sub.3 S:    45.72                                                                            3.84                                                                             19.03                                            (decomp.)                                                                             Found:         45.46                                                                            3.88                                                                             18.97                165   CN     H   H H  CH.sub.3                                                                            240-245° C.                                                                    Calcd. for C.sub.14 H.sub.12 N.sub.6                                          O.sub.2 S:     51.22                                                                            3.68                                                                             25.59                                                                            9.77                                          (decomp.)                                                                             Found:         49.43                                                                            3.58                                                                             24.55                                                                            9.47              166   COCH.sub.3                                                                           H   H H  CH.sub.3                                                                            204-207° C.                                                                    Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.3 S      52.17                                                                            4.38                                                                             20.27                                                                            9.28                                                  Found:         51.82                                                                            4.25                                                                             20.95                                                                            9.19              167   CN     H   H H  F     201-203° C.                                                                    Calcd. for C.sub.13 H.sub.9 FN.sub.6                                          O.sub.2 S:     46.93                                                                            2.73                                                                             25.29                                                    Found:         46.41                                                                            2.81                                                                             26.01                168   CF.sub.3                                                                             H   H H  F     214-216° C.                                                                    Calcd. for C.sub.13 H.sub.9 F.sub.4                                           N.sub.5 O.sub.2 S:                                                                           41.60                                                                            2.42                                                                             18.66                                                    Found:         41.33                                                                            2.61                                                                             18.74                169   CF.sub.3                                                                             H   Cl                                                                              H  H     170-171° C.                                                                    Calcd. for C.sub.13 H.sub.9 ClF.sub.3                                         N.sub.5 O.sub.2 S:                                                                           39.85                                                                            2.32                                                                             17.88                                                    Found:         39.96                                                                            2.29                                                                             17.30                170   Cl     OCH.sub.3                                                                         H H  Cl    229-231° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.3 S                                                                            40.21                                                                            2.86                                                                             18.04                                            (decomp.)                                                                             Found:         40.18                                                                            2.99                                                                             17.71                171   F      H   H H  OCH.sub.3                                                                           212-214° C.                                                                    Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.3 S:     46.28                                                                            3.58                                                                             20.76                                                    Found:         46.26                                                                            3.56                                                                             20.49                172   F      OCH.sub.3                                                                         H H  F     219-221° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                           43.94                                                                            3.12                                                                             19.71                                                    Found:         43.79                                                                            3.29                                                                             19.48                173   F      H   H H  NO.sub.2                                                                            227° C.                                                                        Calcd. for C.sub.12 H.sub.9 FN.sub.6                                          O.sub.2 S:     44.99                                                                            2.83                                                                             26.24                                            (decomp.)                                                                             Found:         44.63                                                                            2.51                                                                             26.46                174   F      CH.sub.3                                                                          H H  F     219-221° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.2 S:                                                                           46.01                                                                            3.27                                                                             20.64                                                    Found:         46.27                                                                            3.47                                                                             20.27                175   CF.sub.3                                                                             H   H H  OCH.sub.3                                                                           209-211° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                           43.41                                                                            3.12                                                                             18.08                                                    Found:         43.31                                                                            3.07                                                                             17.97                176   CF.sub.3                                                                             H   H H  CH.sub.2 SCH.sub.3                                                                  227-229° C.                                                                    Calcd. for C.sub.15 H.sub.14 F.sub.3                                          N.sub.5 O.sub.2 S.sub.2 :                                                                    43.16                                                                            3.38                                                                             16.78                                                    Found:         43.24                                                                            3.71                                                                             16.37                177   CF.sub.3                                                                             H   H H  CH.sub.3                                                                            219-220° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                           48.41                                                                            3.48                                                                             20.17                                                    Found:         48.14                                                                            3.71                                                                             20.34                __________________________________________________________________________

                                      TABLE VII                                   __________________________________________________________________________     ##STR50##                                                                                              Elemental Analysis                                  Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                         Analysis      C  H  N                               __________________________________________________________________________    178   Cl H H H Cl 133°-134.5° C.                                                          Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.3 S:    40.22                                                                            2.83                                                                             18.03                           179   Cl H H H H  195-196° C.                                                                    Found:        40.05                                                                            2.88                                                                             17.86                           __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________     ##STR51##                                                                                                    Elemental Analysis                            Compound                                                                            R.sup.1                                                                             R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          R.sup.5                                                                           Melting Point                                                                         Analysis      C  H  N                         __________________________________________________________________________    180   Cl    H  H H  Cl  268°-269.5° C.                                                          Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          40.24                                                                            2.51                                                                             19.54                                             (decomp.)                                                                             Found:        40.19                                                                            2.68                                                                             19.06                     181   F     H  H H  Cl  270-273° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClFN.sub.5                                        O.sub.2 S:    42.17                                                                            2.65                                                                             20.49                                                     Found:        42.09                                                                            2.63                                                                             19.91                     182   Cl    CH.sub.3                                                                         H H  Cl  257-163°  C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          41.91                                                                            2.98                                                                             18.82                                                     Found:        41.88                                                                            2.86                                                                             18.30                     183   CF.sub.3                                                                            H  H H  H   171-185° C.                                                                    Calcd. for C.sub.13 H.sub.10 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                          43.70                                                                            2.82                                                                             19.60                                                     Found:        42.33                                                                            2.66                                                                             19.36                     184   NO.sub.2                                                                            H  H H  CH.sub.3                                                                          200-205° C.                                                                    Calcd. for C.sub.13 H.sub.12 N.sub.6                                          O.sub.4 S:    44.82                                                                            3.47                                                                             24.13                                                     Found:        44.43                                                                            3.43                                                                             23.81                     185   F     H  H H  F   255-257° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2                                           N.sub.5 O.sub.2 S:                                                                          44.30                                                                            2.79                                                                             21.53                                                     Found:        44.08                                                                            3.08                                                                             21.32                     186   Cl    H  H H  CH.sub.3                                                                          229.5-233° C.                                                                  Calcd. for C.sub.13 H.sub.12 ClN.sub.5                                        O.sub.2 S:    46.22                                                                            3.58                                                                             20.74                                                     Found:        45.56                                                                            3.93                                                                             20.27                     187   COOCH.sub.3                                                                         H  H H  F   200-201° C.                                                                    Calcd. for C.sub.14 H.sub.12 FN.sub.5                                         O.sub.4 S:    46.03                                                                            3.31                                                                             19.17                                                     Found:        45.75                                                                            3.25                                                                             19.20                     188   NO.sub.2                                                                            H  H CH.sub.3                                                                         CH.sub.3                                                                          233-236° C.                                                                    Calcd. for C.sub.14 H.sub.14 N.sub.6                                          O.sub.4 S:    46.40                                                                            3.89                                                                             23.19                                                     Found:        46.29                                                                            3.67                                                                             22.84                     189   COOCH.sub.3                                                                         H  H H  CH.sub.3                                                                          167-167.5° C.                                                                  Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.4 S:    49.86                                                                            4.18                                                                             19.38                                                     Found:        49.78                                                                            4.10                                                                             19.16                     190   F     CH.sub.3                                                                         H H  F   256-258° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.2 S:                                                                          46.02                                                                            3.27                                                                             20.64                                                     Found:        44.95                                                                            3.00                                                                             20.00                     191   CF.sub.3                                                                            H  H H  OCH.sub.3                                                                         260-262° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                          43.41                                                                            3.12                                                                             18.08                                                     Found:        42.83                                                                            3.18                                                                             19.74                     __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________     ##STR52##                                                                                                 Elemental Analysis                               Compound                                                                            R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                         Analysis      C  H  N  S                         __________________________________________________________________________    192   Cl   H  H H Cl 249° C.                                                                        Calcd. for C.sub.12 H.sub.10 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          40.21                                                                            2.51                                                                             19.56                                                                            8.94                                           (decomp.)                                                                             Found:        39.99                                                                            2.66                                                                             19.62                                                                            8.70                      193   F    H  H H F  263-265° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2 N.sub.5                                   O.sub.2 S:    44.30                                                                            2.79                                                                             21.53                                                                            9.86                                                   Found:        44.37                                                                            2.92                                                                             20.98                                                                            9.85                      194   Cl   CH.sub.3                                                                         H H Cl 276-280° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          41.94                                                                            2.98                                                                             18.82                                                                            8.61                                                   Found:        41.59                                                                            2.97                                                                             19.13                                                                            8.46                      195   Cl   H  H H CH.sub.3                                                                         227-232° C.                                                                    Calcd. for C.sub.13 H.sub.12 ClN.sub.5                                        O.sub.2 S:    46.22                                                                            3.58                                                                             20.74                                                                            9.49                                                   Found:        45.73                                                                            3.47                                                                             20.94                                                                            9.49                      196   NO.sub.2                                                                           H  H H CH.sub.3                                                                         251-253° C.                                                                    Calcd. for C.sub.13 H.sub.12 N.sub.6 O.sub.4                                  S:            44.82                                                                            3.47                                                                             24.13                                                                            9.20                                                   Found:        43.84                                                                            3.39                                                                             24.05                                                                            9.28                      197   COOMe                                                                              H  H H CH.sub.3                                                                         208.5-210.5° C.                                                                Calcd. for C.sub.15 H.sub.15 N.sub.5 O.sub.4                                  S:            49.85                                                                            4.18                                                                             19.38                                                     Found:        49.96                                                                            4.14                                                                             19.75                        __________________________________________________________________________

                                      TABLE X                                     __________________________________________________________________________     ##STR53##                                                                                            Elemental Analysis                                    Compound                                                                            R.sup.1                                                                         R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                 __________________________________________________________________________    198   Cl                                                                              H  H H H 174-176° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S:    41.95                                                                            2.98                                                                             18.82                                                     Found:        41.64                                                                            2.84                                                                             18.54                             199   Cl                                                                              CH.sub.3                                                                         H H Cl                                                                              231-233° C.                                                                   Calcd. for C.sub.14 H.sub.12 Cl.sub.3 N.sub.5                                 O.sub.2 S:    39.96                                                                            2.88                                                                             18.65                                                     Found:        39.94                                                                            2.88                                                                             18.15                             200   Cl                                                                              H  H H Cl                                                                              171° C.                                                                       Calcd. for C.sub.13 H.sub.10 Cl.sub.3 N.sub.5                                 O.sub.2 S:    38.39                                                                            2.48                                                                             17.22                                              (decomp.)                                                                            Found:        38.47                                                                            2.66                                                                             17.37                             __________________________________________________________________________

                                      TABLE XI                                    __________________________________________________________________________     ##STR54##                                                                                             Elemental Analysis                                   Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                                __________________________________________________________________________    201   CF.sub.3                                                                         H H H H  75-78° C.                                                                     Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5                                  O.sub.3 S:    43.36                                                                            3.09                                                                             18.06                                              (decomp.)                                                                            Found:        43.53                                                                            3.17                                                                             17.50                            202   Cl H H H CH.sub.3                                                                         105-110° C.                                                                   Calcd. for C.sub.14 H.sub.14 ClN.sub.5 O.sub.3                                S:            45.66                                                                            3.80                                                                             19.02                                              (decomp.)                                                                            Found:        43.74                                                                            3.80                                                                             18.76                            203   Cl H H H Cl 215-216°  C.                                                                  Calcd. for C.sub.12 H.sub.12 Cl.sub.2 N.sub.5                                 O.sub.2 S:    40.21                                                                            2.83                                                                             18.04                                                     Found:        40.13                                                                            2.96                                                                             17.99                            __________________________________________________________________________

                                      TABLE XII                                   __________________________________________________________________________     ##STR55##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N  S                               __________________________________________________________________________    204   Cl                                                                              H H H Cl                                                                              214-216° C.                                                                   Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:    43.51                                                                            3.37                                                                             18.13                                                                            8.30                                                   Found:        43.50                                                                            3.28                                                                             17.63                                                                            7.96                            __________________________________________________________________________

                                      TABLE XIII                                  __________________________________________________________________________     ##STR56##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    205   Cl                                                                              H H H Cl                                                                              235-237° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S:    41.93                                                                            2.95                                                                             18.81                                                     Found:        41.80                                                                            3.08                                                                             18.65                              __________________________________________________________________________

                                      TABLE XIV                                   __________________________________________________________________________     ##STR57##                                                                    Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Elemental Analysis                                     __________________________________________________________________________    206   Cl                                                                              H H H Cl                                                                              215-216° C.                                                                   Exact mass calcd for C.sub.12 H.sub.8 BrCl.sub.2                              N.sub.5 O.sub.2 S: 438.8898                                                   Found:             438.8899                            __________________________________________________________________________

                                      TABLE XV                                    __________________________________________________________________________     ##STR58##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    207   Cl                                                                              H H H Cl                                                                              105-110° C.                                                                   Calcd. for C.sub.12 H.sub.8 Cl.sub.3 N.sub.5                                  O.sub.2 S:    36.69                                                                            2.04                                                                             17.80                                                     Found:        36.28                                                                            2.15                                                                             18.41                              __________________________________________________________________________

                                      TABLE XVI                                   __________________________________________________________________________     ##STR59##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  N  H                                  __________________________________________________________________________    208   Cl                                                                              H H H Cl                                                                              235-237° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.3 S:    38.51                                                                            2.41                                                                             18.72                                                     Found:        38.29                                                                            2.44                                                                             18.92                              __________________________________________________________________________

                                      TABLE XVII                                  __________________________________________________________________________     ##STR60##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                 __________________________________________________________________________    209   Cl                                                                              H H H Cl                                                                              266-269° C.                                                                   Calcd. for C.sub.13 H.sub.8 Cl.sub.2 F.sub.3                                  N.sub.5 O.sub.3 S:                                                                           35.29                                                                            1.81                                                                             15.84                                                    Found:         35.14                                                                            1.72                                                                             15.65                             __________________________________________________________________________

                                      TABLE XVIII                                 __________________________________________________________________________     ##STR61##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    210   Cl                                                                              H H H Cl                                                                              230-233° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.3 S:    40.21                                                                            2.83                                                                             18.03                                                     Found:        40.10                                                                            2.76                                                                             17.87                              __________________________________________________________________________

                                      TABLE XIX                                   __________________________________________________________________________     ##STR62##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    211   Cl                                                                              H H H Cl                                                                              239-243° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.2 S.sub.2 :                                                                           36.92                                                                            2.31                                                                             17.95                                              (decomp.)                                                                            Found:        36.51                                                                            2.41                                                                             17.68                              __________________________________________________________________________

                                      TABLE XX                                    __________________________________________________________________________     ##STR63##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  N  H  S                               __________________________________________________________________________    212   Cl                                                                              H H H Cl                                                                              310° C.                                                                       Calcd. for C.sub.13 H.sub.12 Cl.sub.2 N.sub.6                                 O.sub.2 S:    40.31                                                                            3.10                                                                             21.71                                                                            8.28                                                   Found:        40.31                                                                            3.05                                                                             22.31                                                                            7.99                            __________________________________________________________________________

                                      TABLE XXI                                   __________________________________________________________________________     ##STR64##                                                                                                   Elemental Analysis                             Compound                                                                            R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          R.sup.5                                                                           Melting Point                                                                         Analysis      C  H  N                          __________________________________________________________________________    213   Cl   H  H H  Cl  235-242° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.3 S:                                                                          40.21                                                                            2.84                                                                             18.04                                             (decomp.)                                                                             Found:        40.37                                                                            2.78                                                                             18.06                      214   F    H  H H  F   230-232° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                          43.94                                                                            3.12                                                                             19.71                                                     Found:        43.80                                                                            3.10                                                                             20.11                      215   COOCH.sub.3                                                                        H  H H  F   195-197° C.                                                                    Calcd. for C.sub.15 H.sub.14 FN.sub.5                                         O.sub.5 S:    45.57                                                                            3.57                                                                             17.71                                                     Found:        45.26                                                                            3.51                                                                             18.12                      216   COOCH.sub.3                                                                        H  H H  CH.sub.3                                                                          197-198° C.                                                                    Calcd. for C.sub.16 H.sub.17 N.sub.5                                          O.sub.5 S:    49.10                                                                            4.38                                                                             17.89                                                     Found:        48.95                                                                            4.28                                                                             17.88                      217   CF.sub.3                                                                           H  H H  H   213-215° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                          43.41                                                                            3.12                                                                             18.08                                                     Found:        42.90                                                                            3.21                                                                             18.48                      218   Cl   CH.sub.3                                                                         H H  Cl  240.5-241.5° C.                                                                Calcd. for C.sub.14 H.sub.13 Cl.sub.2                                         N.sub.5 O.sub.3 S:                                                                          41.80                                                                            3.26                                                                             17.41                                                     Found:        41.64                                                                            3.28                                                                             17.56                      219   F    CH.sub.3                                                                         H H  F   230-231° C.                                                                    Calcd. for C.sub.14 H.sub.13 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                          45.53                                                                            3.55                                                                             18.96                                                     Found:        45.16                                                                            3.55                                                                             19.37                      220   Cl   H  H H  CH.sub.3                                                                          213-214° C.                                                                    Calcd. for C.sub.14 H.sub. 14 ClN.sub.5                                       O.sub.3 S:    45.72                                                                            3.84                                                                             19.04                                                     Found:        45.96                                                                            3.90                                                                             19.40                      221   NO.sub.2                                                                           H  H H  CH.sub.3                                                                          226-228° C.                                                                    Calcd. for C.sub.14 H.sub.14 N.sub.6                                          O.sub.5 S:    44.44                                                                            3.73                                                                             22.21                                                     Found:        44.52                                                                            3.75                                                                             22.50                      222   NO.sub.2                                                                           H  H CH.sub.3                                                                         CH.sub.3                                                                          230-231° C.                                                                    Calcd. for C.sub.15 H.sub.16 N.sub.6                                          O.sub.5 S:    45.91                                                                            4.11                                                                             21.42                                                     Found:        45.49                                                                            4.04                                                                             21.64                      223   CF.sub.3                                                                           H  H H  OCH.sub.3                                                                         232-233° C.                                                                    Calcd. for C.sub.15 H.sub.14 F.sub.3                                          N.sub.5 O.sub.4 S:                                                                          43.17                                                                            3.38                                                                             16.78                                                     Found:        43.10                                                                            3.42                                                                             16.92                      __________________________________________________________________________

                                      TABLE XXII                                  __________________________________________________________________________     ##STR65##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    224   Cl                                                                              H H H Cl                                                                              220° C.                                                                       Calcd. for C.sub.13 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.4 S:    38.80                                                                            2.24                                                                             17.41                                              (decomp.)                                                                            Found:        39.30                                                                            2.66                                                                             17.41                              __________________________________________________________________________

                                      TABLE XXIII                                 __________________________________________________________________________     ##STR66##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    225   Cl                                                                              H H H Cl                                                                              310-320° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2 N.sub.5                                  O.sub.3 S:    36.65                                                                            1.94                                                                             19.40                                              (decomp.)                                                                            Found:        36.79                                                                            1.76                                                                             19.14                              __________________________________________________________________________

                                      TABLE XXIV                                  __________________________________________________________________________     ##STR67##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    225   Cl                                                                              H H H Cl                                                                              285-287° C.                                                                   Calcd. for C.sub.17 H.sub.10 Cl.sub.2 N.sub.6                                 O.sub.4 S:    43.84                                                                            2.15                                                                             18.00                                                     Found:        44.12                                                                            2.43                                                                             17.45                              __________________________________________________________________________

                                      TABLE XXV                                   __________________________________________________________________________     ##STR68##                                                                                            Elemental Analysis                                    Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis       C  H  N                                __________________________________________________________________________    227   Cl                                                                              H H H Cl 237-239° C.                                                                   Calcd. for C.sub.13 H.sub.8 Cl.sub.2 F.sub.3                                  N.sub.5 O.sub.2 S:                                                                           36.63                                                                            1.88                                                                             16.42                                                    Found:         36.74                                                                            1.52                                                                             16.94                            228   F H H H F  234-237° C.                                                                   Calcd. for C.sub.13 H.sub.8 F.sub.5 N.sub.5                                   O.sub.2 S:     39.74                                                                            2.04                                                                             17.83                                                    Found:         39.49                                                                            2.08                                                                             18.11                            229   Cl                                                                              CH.sub.3                                                                        H H Cl 252-254° C.                                                                   Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3                                 N.sub.5 O.sub.2 S:                                                                           38.21                                                                            2.27                                                                             15.97                                                    Found:         38.09                                                                            2.34                                                                             16.40                            230   F CH.sub.3                                                                        H H F  243-245° C.                                                                   Calcd. for C.sub.14 H.sub.10 F.sub.5 N.sub.5                                  O.sub.2 S:     41.32                                                                            2.46                                                                             17.23                                                    Found:         41.21                                                                            2.51                                                                             17.49                            231   CF.sub.3                                                                        H H H OCH.sub.3                                                                        226-229° C.                                                                   Calcd. for C.sub.15 H.sub.11 F.sub.6 N.sub.5                                  O.sub.3 S:     39.61                                                                            2.42                                                                             15.40                                                    Found:         39.50                                                                            2.52                                                                             15.60                            __________________________________________________________________________

                                      TABLE XXVI                                  __________________________________________________________________________     ##STR69##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    232   Cl                                                                              H H H Cl                                                                              >310° C.                                                                      Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.3 S:    38.51                                                                            2.41                                                                             18.72                                                     Found:        38.28                                                                            2.44                                                                             19.03                              __________________________________________________________________________

                                      TABLE XXVII                                 __________________________________________________________________________     ##STR70##                                                                                            Elemental Analysis                                    Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                                 __________________________________________________________________________    233   Cl                                                                              H H H CH.sub.3                                                                         221-224° C.                                                                   Calcd. for C.sub.15 H.sub.14 ClN.sub.5 O.sub.2                                S:            49.52                                                                            3.85                                                                             19.27                                              (decomp.)                                                                            Found:        49.56                                                                            3.85                                                                             18.90                             __________________________________________________________________________

                                      TABLE XXVIII                                __________________________________________________________________________     ##STR71##                                                                    Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Elemental Analysis                                     __________________________________________________________________________    234   Cl                                                                              H H H Cl                                                                              80-92° C.                                                                     Exact mass calcd. for C.sub.13 H.sub.11 Cl.sub.2                              N.sub.5 O.sub.2 S: 327.9981                                            (decomp)                                                                             Found:             327.9994                            __________________________________________________________________________

                                      TABLE XXIX                                  __________________________________________________________________________     ##STR72##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    235   Cl                                                                              H H H Cl                                                                              254-258° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S.sub.2 :                                                                           36.96                                                                            2.60                                                                             16.58                                              (decomp.)                                                                            Found:        36.92                                                                            2.44                                                                             16.57                              __________________________________________________________________________

                                      TABLE XXX                                   __________________________________________________________________________     ##STR73##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                 __________________________________________________________________________    236   Cl                                                                              H H H Cl                                                                              250-253° C.                                                                   Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3                                 N.sub.5 O.sub.3 S:                                                                           36.85                                                                            2.19                                                                             15.35                                             (decomp.)                                                                            Found:         36.44                                                                            2.07                                                                             15.62                             __________________________________________________________________________

                                      TABLE XXXI                                  __________________________________________________________________________     ##STR74##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    237   Cl                                                                              H H H Cl                                                                              270-274° C.                                                                   Calcd. for C.sub.14 H.sub.14 Cl.sub.2 N.sub.6                                 O.sub.2 S:    41.89                                                                            3.49                                                                             20.95                                              (decomp.)                                                                            Found:        41.87                                                                            3.49                                                                             21.03                              __________________________________________________________________________

                                      TABLE XXXII                                 __________________________________________________________________________     ##STR75##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                 __________________________________________________________________________    238   Cl                                                                              H H H Cl                                                                              286-287° C.                                                                   Calcd. for C.sub.13 H.sub.5 Cl.sub.2 F.sub.6                                  N.sub.5 O.sub.2 S:                                                                           32.56                                                                            1.04                                                                             14.59                                                    Found:         32.98                                                                            0.70                                                                             14.71                             __________________________________________________________________________

                                      TABLE XXXIII                                __________________________________________________________________________     ##STR76##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    239   Cl                                                                              H H H Cl                                                                              284-286° C.                                                                   Calcd. for C.sub.20 H.sub.21 Cl.sub.2 N.sub.5                                 O.sub.3 S:    49.90                                                                            4.36                                                                             14.52                                                     Found:        49.81                                                                            4.22                                                                             14.28                              __________________________________________________________________________

                                      TABLE XXXIV                                 __________________________________________________________________________     ##STR77##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    240   Cl                                                                              H H H Cl                                                                              236-239° C.                                                                   Calcd. for C.sub.15 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.4 S:    41.86                                                                            3.02                                                                             16.28                                              (decomp.)                                                                            Found:        41.75                                                                            2.79                                                                             16.16                              __________________________________________________________________________

                                      TABLE XXXV                                  __________________________________________________________________________     ##STR78##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis        C  H  N                                __________________________________________________________________________    241   Cl                                                                              H H H Cl                                                                              120-130° C.                                                                   Calcd. for C.sub.13 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.4 S.H.sub.2 O                                                                           37.15                                                                            2.38                                                                             16.70                                            (decomp.)                                                                            Found:          37.03                                                                            2.02                                                                             17.16                            __________________________________________________________________________

                                      TABLE XXXVI                                 __________________________________________________________________________     ##STR79##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    242   Cl                                                                              H H H Cl                                                                              280-304° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.3 S:    38.51                                                                            2.41                                                                             18.72                                              (decomp.)                                                                            Found:        38.52                                                                            2.49                                                                             19.03                              __________________________________________________________________________

                                      TABLE XXXVII                                __________________________________________________________________________     ##STR80##                                                                                           Elemental Analysis                                     Compound                                                                            R.sup.1                                                                         R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    243   Cl                                                                              CH.sub.3                                                                         H CH.sub.3                                                                         303-306° C.                                                                   Calcd. for C.sub.17 H.sub.14 ClN.sub.5 O.sub.2                                              52.65                                                                            3.64                                                                             18.05                                              (decomp.)                                                                            Found:        52.10                                                                            3.65                                                                             18.51                              244   Cl                                                                              H  H CH.sub.3                                                                         262-265° C.                                                                   Calcd. for C.sub.16 H.sub.12 ClN.sub.5 O.sub.2                                              51.41                                                                            3.24                                                                             18.73                                              (decomp.)                                                                            Found:        50.97                                                                            3.29                                                                             18.99                              __________________________________________________________________________

                                      TABLE XXXVIII                               __________________________________________________________________________     ##STR81##                                                                                              Elemental Analysis                                  Compound                                                                            R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          Melting Point                                                                        Analysis        C  H  N                             __________________________________________________________________________    245   COOMe                                                                              CH.sub.3                                                                         H  CH.sub.3                                                                        206-208° C.                                                                   Calcd. for C.sub.19 H.sub.17 N.sub.5 O.sub.4                                  S.1/2H.sub.2 O: 54.28                                                                            4.32                                                                             16.65                                                   Found:          53.98                                                                            4.12                                                                             16.83                         __________________________________________________________________________

                                      TABLE XXXIX                                 __________________________________________________________________________     ##STR82##                                                                                                    Elemental Analysis                            Compound                                                                            R.sup.1                                                                          R.sup.2                                                                            R.sup.3                                                                            R.sup.4                                                                          R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                         __________________________________________________________________________    246   CH.sub.3                                                                         CF.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                         273-274° C.                                                                   Calcd. for C.sub.12 H.sub.12 F.sub.3                                          N.sub.7 O.sub.2 S:                                                                          38.39                                                                            3.22                                                                             26.12                                              (decomp.)                                                                            Found:        38.73                                                                            3.23                                                                             25.92                     247   CH.sub.3                                                                         CF.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         288-288.5° C.                                                                 Calcd. for C.sub.13 H.sub.14 F.sub.3                                          N.sub.7 O.sub.2 S:                                                                          40.09                                                                            3.62                                                                             25.18                                              (decomp.)                                                                            Found:        40.22                                                                            3.58                                                                             25.61                     248   CH.sub.3                                                                         COOMe                                                                              CH.sub.3                                                                           H  CH.sub.3                                                                         174-175° C.                                                                   Calcd. for C.sub.13 H.sub.15 N.sub.7                                          O.sub.4 S:    42.73                                                                            4.14                                                                             26.84                                                     Found:        42.39                                                                            4.21                                                                             26.91                     249   CH.sub.3                                                                         COOMe                                                                              CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         208-210° C.                                                                   Calcd. for C.sub.14 H.sub.17 N.sub.7                                          O.sub.4 S:    44.32                                                                            4.52                                                                             25.85                                                     Found:        44.07                                                                            4.31                                                                             25.72                     250   CH.sub.3                                                                         CH.sub.3                                                                           COOMe                                                                              CH.sub.3                                                                         CH.sub.3                                                                         228-230° C.                                                                   Calcd. for C.sub.14 H.sub.17 N.sub.7                                          O.sub.4 S:    44.32                                                                            4.52                                                                             25.85                                                     Found:        44.06                                                                            4.82                                                                             25.97                     __________________________________________________________________________

                                      TABLE XL                                    __________________________________________________________________________     ##STR83##                                                                    Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                          R.sup.4                                                                         Melting Point                                                                           Elemental Analysis                                  __________________________________________________________________________    251   Cl H Cl H 159°-161° C.                                                              Exact mass calcd. for C.sub.12 H.sub.10                                       Cl.sub.2 N.sub.6 O.sub.2 S:                                                                      371.9963                                                   Found:             371.9973                                                   Analysis       C  H  N                              252   Cl H H  H >210° C. (decomp)                                                                Calcd. for C.sub.12 H.sub.11 ClN.sub.6 O.sub.2                                S:             42.55                                                                            3.27                                                                             24.80                                                    Found:         42.19                                                                            3.28                                                                             24.27                          __________________________________________________________________________

                                      TABLE XLI                                   __________________________________________________________________________     ##STR84##                                                                                             Elemental Analysis                                   Compound                                                                            R.sup.1                                                                         R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         Melting Point                                                                           Analysis       C  H  N                               __________________________________________________________________________    253   H H  H H >250° C. (decomp)                                                                Calcd. for C.sub.12 H.sub.12 N.sub.6 O.sub.2                                  S.H.sub.2 O:   44.72                                                                            4.38                                                                             26.06                                                    Found:         44.88                                                                            4.19                                                                             26.37                           254   H Cl H H >260° C. (decomp)                                                                Calcd. for C.sub.12 H.sub.11 ClN.sub.6 O.sub.2                                S:             42.55                                                                            3.27                                                                             24.80                                                    Found:         42.48                                                                            3.40                                                                             24.49                           __________________________________________________________________________

                                      TABLE XLII                                  __________________________________________________________________________     ##STR85##                                                                    Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         Melting Point                                                                          Elemental Analysis                                    __________________________________________________________________________    255   Cl H H H 207.5°-208.5° C.                                                        Exact mass calcd. for C.sub.12 H.sub.11 ClN.sub.6                             O.sub.2 S:         338.0352                                                   Found:             338.0342                            __________________________________________________________________________

                                      TABLE XLIII                                 __________________________________________________________________________     ##STR86##                                                                                           Elemental Analysis                                     Compound                                                                            Ar        Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    256                                                                                  ##STR87##                                                                              120-125° C.                                                                   Calcd. for C.sub.10 H.sub.10 N.sub.6 O.sub.2                                  S.sub.2 : Found:                                                                            38.66 38.48                                                                      3.22 3.28                                                                        27.06 26.92                        257                                                                                  ##STR88##                                                                              160-168° C.                                                                   Calcd. for C.sub.13 H.sub.13 N.sub.5 O.sub.4                                  S.sub.2 Found:                                                                              42.49 42.04                                                                      3.53 3.40                                                                        19.05 18.81                        258                                                                                  ##STR89##                                                                              224-226° C. (decomp)                                                          Calcd. for C.sub.14 H.sub.11 ClN.sub.6 O.sub.2                                S.sub.2 : Found:                                                                            42.58 43.10                                                                      2.78 2.79                                                                        21.27 20.74                        259                                                                                  ##STR90##                                                                              195° C. (decomp.)                                                             Calcd. for C.sub.13 H.sub.11 N.sub.8 O.sub.2 S:                               Found:        47.41 47.01                                                                      3.37 3.31                                                                        29.78 30.78                        __________________________________________________________________________

    TABLE XLIV      ##STR91##       Elemental Analysis Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5     Melting Point Analysis C H N Cl S       260 Cl Cl CH.sub.3 CH.sub.3 CH.sub.3 220-222° C. Calcd. for     C.sub.14 H.sub.13 Cl.sub.2 N.sub.5 O.sub.2 S: 43.54 3.39 18.13     Found: 43.55 3.32 18.03 261 COOMe CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     175.5-177° C.   Calcd. for C.sub.17 H.sub.19 N.sub.5 O.sub.4 S:     52.43 4.92 17.98        Found: 52.31 4.93 17.94 262 Cl Cl COCH.sub.3     CH.sub.3 CH.sub.3 214-217° C. Calcd. for C.sub.15 H.sub.13     Cl.sub.2 N.sub.5 O.sub.3 S: 43.49 3.16 16.90        Found: 43.44 3.16     16.77 263 Cl Cl CH.sub.2 CHCH.sub.2 CH.sub.3 CH.sub.3 182-184° C.     Calcd. for C.sub.16 H.sub.15 Cl.sub.2 N.sub.5 O.sub.2 S: 46.61 3.67     16.98        Found: 46.74 3.67 16.86 264 Cl Cl CH.sub.2 COOEt CH.sub.3     CH.sub.3 173-176° C. Calcd. for C.sub.17 H.sub.17 Cl.sub.2     N.sub.5 O.sub.4 S: 44.55 3.74 15.27        Found: 44.74 3.74 15.08 265     Cl Cl CH.sub.2 Ph CH.sub.3 CH.sub.3 >240° C. Calcd. for C.sub.20     H.sub.17 Cl.sub.2 N.sub.5 O.sub.2 S.1/2H.sub.2 O: 50.97 3.85 14.85     (decomp.) Found: 50.93 3.66 14.85 266 COOMe CH.sub.3 CH.sub.2 COOEt     CH.sub.3 CH.sub.3 152-155° C. Calcd. for C.sub.20 H.sub.23     N.sub.5 O.sub.6 S: 52.05 5.02 15.17        Found: 51.64 4.94 15.39 267     COOMe CH.sub.3 CH.sub.2 Ph CH.sub.3 CH.sub.3 174-176° C. Calcd.     for C.sub.23 H.sub.23 N.sub.5 O.sub.4 S: 59.34 4.98 15.04        Found:     59.00 4.89 15.18 268 Cl Cl COCH.sub.3 H CH.sub.3 176-181° C.     Calcd. for C.sub.14 H.sub.11 Cl.sub.2 N.sub.5 O.sub.3 S: 42.02 2.77     17.49        Found: 42.28 2.90 17.16 269 Cl Cl CO.sub.-iPr H CH.sub.3     193-194°5 C. Calcd. for C.sub.16 H.sub.15 Cl.sub.2 N.sub.5     O.sub.3 S: 44.87 3.53 16.35        Found: 45.26 3.53 16.39 270 Cl Cl     COC.sub.11 H.sub.23  CH.sub.3 105.5-106.5° C. Calcd. for C.sub.24     H.sub.31 Cl.sub.2 N.sub.5 O.sub.3 S: 53.33 5.78 12.96        Found:     53.40 5.77 12.84      271 Cl Cl     ##STR92##      H CH.sub.3 234-235°  C.  Calcd. for C.sub.19 H.sub.11 Cl.sub.4     N.sub.5 O.sub.3 S:Found: 42.9643.31 2.092.29 13.1813.04  272 Cl Cl     CO.sub.2 Et H CH.sub.3 189-191° C. Calcd. for C.sub.15 H.sub.15     Cl.sub.2 N.sub.5 O.sub.4 S: 41.87 3.05 16.28        Found: 42.51 3.25     16.02 273 Cl Cl CON(CH.sub.3).sub.2 H CH.sub.3 225-228° C. Calcd.     for C.sub.15 H.sub.14 Cl.sub.2 N.sub.6 O.sub.3 S: 41.97 3.29 19.58     (decomp.) Found: 42.08 3.27 20.18 274 Cl Cl COPh H CH.sub.3 187-189.degre     e. C. Calcd. for C.sub.19 H.sub.13 Cl.sub.2 N.sub.5 O.sub.3 S: 49.36     2.83 15.15        Found: 48.97 2.84 15.16 275 F F COCH.sub.3 H CH.sub.3     195-200° C. Calcd. for C.sub.14 H.sub.11 F.sub.2 N.sub.5 O.sub.3     S: 45.77 3.02 19.07  8.73        Found: 45.59 3.12 19.16  8.91 276 F F     COEt H CH.sub.3 154-160°  C. Calcd. for C.sub.15 H.sub.13 F.sub.2     N.sub.5 O.sub.3 S: 47.24 3.44 18.37  8.41        Found: 47.05 3.44 18.49      8.27 277 F F COiPr H CH.sub.3 182-184° C. Calcd. for C.sub.16     H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 48.60 3.82 17.71        Found: 48.41     3.93 17.43 278 F F COCH.sub.2 tBu H CH.sub.3 158-162° C. Calcd.     for C.sub.18 H.sub.19 F.sub.2 N.sub.5 O.sub.3 S: 51.05 4.52 16.54  7.57           Found: 51.15 4.62 16.38  7.83 279 F F COnBu H CH.sub.3 131-134.degr     ee. C. Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3 S: 49.87     4.19 17.11        Found: 49.10 4.04 17.05 280 F F COtBu H CH.sub.3     185-186° C. Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3     S: 49.87 4.19 17.11  7.83       (decomp.) Found: 49.93 3.89 16.82  7.10     281 F F COCH.sub.2 Ph H CH.sub.3 178-185°  C. Calcd. for C.sub.20     H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 54.17 3.41 15.80        Found: 53.60     3.18 15.56 282 F F COCH.sub.2 CH.sub.2 Cl H CH.sub.3 195° C.     Calcd. for C.sub.15 H.sub.12 ClF.sub.2 N.sub.5 O.sub.3 S: 43.33 2.91     16.84 8.53 7.71       (decomp.) Found: 43.21 2.95 17.31 8.45 7.47 283 F     F COnPr H CH.sub.3 130-135° C. Calcd. for C.sub.16 H.sub.15     F.sub.2 N.sub.5 O.sub.3 S: 48.60 3.82 17.71  8.11        Found: 48.42     3.81 17.91 7.98 284 F F COCH.sub.2 iPr H CH.sub.3 154-159° C.     Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3 S: 49.87 4.19 17.11      7.83        Found: 49.45 4.04 17.15  7.68 285 F F COCH.sub.2 Cl H     CH.sub.3 156-158° C. Calcd. for C.sub.14 H.sub.10 ClF.sub.2     N.sub.5 O.sub.3 S: 41.85 2.51 17.43        Found: 42.19 2.68 17.43 286 F     F COCHCH.sub. 3CH.sub.2 H CH.sub.3 171.5-174° C.   Calcd. for     C.sub.16 H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81  8.15       Found: 48.36 3.51 17.91  7.94 287 F F COnC.sub.9 H.sub.19 H CH.sub.3     97-99° C. Calcd. for C.sub.22 H.sub.27 F.sub.2 N.sub.5 O.sub.3 S:     55.10 5.68 14.61  6.69        Found: 55.22 5.60 14.85  6.63 288 F F     COCHCHCH.sub.3 H CH.sub.3 154-156° C. Calcd. for C.sub.16     H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81 8.15        Found:     48.41 3.41 17.94 8.49 289 F F COcycloC.sub.3      H.sub.5 H CH.sub.3 200.5-203° C.   Calcd. for C.sub.16 H.sub.13     F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81  8.15        Found: 48.32     3.34 18.03  8.34 290 F F COPh H CH.sub.3 186-189° C. Calcd. for     C.sub.19 H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 53.14 3.05 16.31  7.47       Found: 53.74 3.16 16.63  7.11 291 F F COcycloC.sub.6 H.sub.11 H     CH.sub.3 178- 180° C. Calcd. for C.sub.19 H.sub.19 F.sub.2     N.sub.5 O.sub.3 S: 52.40 4.40 16.08  7.36        Found: 51.40 4.28 16.08      7.78 292 F F COCH.sub.2 OPh H CH.sub.3 141-144° C. Calcd. for     C.sub.20 H.sub.15 F.sub.2 N.sub.5 O.sub.4 S: 52.28 3.29 15.25  6.98       Found: 51.77 3.38 15.28  6.76 293 F F COCHCHPh H CH.sub.3 oil Calcd.     for C.sub.21 H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 55.38 3.32 15.38  7.04           Found: 55.55 3.45 15.29  6.98 294 F F COCH.sub.2 CH.sub.2 CO.sub.2     CH.sub.2 CH.sub.3 H CH.sub.3 157-162° C. Calcd. for C.sub.18     H.sub.17 F.sub.2 N.sub.5 O.sub.5 S: 47.68 3.78 15.45  7.07        Found:     47.32 3.78 15.68  7.03 295 F F CO(2-furyl) H CH.sub.3 120° C.     Calcd. for C.sub. 17 H.sub.11 F.sub.2 N.sub.5 O.sub.4 S: 48.69 2.64     16.70 7.65       (decomp.) Found: 48.49 2.75 17.03  7.83 296 F F     COcycloC.sub.4 H.sub.7 H CH.sub.3 161-170° C. Calcd. for C.sub.17     H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 50.12 3.71 17.19  7.87        Found:     49.58 3.89 17.21  8.07 297 F F SO.sub.2      CH.sub.3 H CH.sub.3 193-195° C. Calcd. for C.sub.13 H.sub.11     F.sub.2 N.sub.5 O.sub.4 S.sub.2 : 38.71 2.75 17.36  15.90        Found:     38.98 2.92 17.18  15.72 298 F F SO.sub.2 Ph H CH.sub.3 182-190°     C. Calcd. for C.sub.18 H.sub.13 F.sub.2 N.sub.5 O.sub.4 S.sub.2 : 46.45     2.82 15.05  13.78        Found: 46.41 3.03 14.79  14.01 299 F F CH.sub.2     Ph H CH.sub.3 170-177° C. Calcd. for C.sub.9 H.sub.15 F.sub.2     N.sub.5 O.sub.2 S: 54.93 3.64 16.86  7.72        Found: 54.45 3.73 16.63      7.77 300 F F CO(SEt) H CH.sub.3 197-199° C. Calcd. for C.sub.15     H.sub.13 F.sub.2 N.sub.5 O.sub.3 S.sub.2 : 43.58 3.17 16.94  15.51      Found: 43.45 3.19 17.12  15.64 301 F F CH.sub.2 (4-NO.sub.2 Ph) H     CH.sub.3 194-200° C. Calcd. for C.sub.19 H.sub.14 F.sub.2 N.sub.6     O.sub.4 S: 49.64 3.07 18.26  6.96        Found: 49.64 3.25 18.40  6.88     302 F F CH.sub.2 (4-MeOPh) H CH.sub.3 156-158° C. Calcd. for     C.sub.20 H.sub.17 F.sub.2 N.sub.5 O.sub.3 S: 53.92 3.85 15.72  7.20       Found: 53.65 3.98 15.95  7.46 303 F F CH.sub.2 (2-furyl) H CH.sub.3     177-180° C. Calcd. for C.sub.17 H.sub.13 F.sub.2 N.sub.5 O.sub.3     S: 50.37 3.23 17.28  7.91        Found: 50.50 3.30 17.33  7.74

                                      TABLE XLV                                   __________________________________________________________________________     ##STR93##                                                                    Compound                                                                            R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                          R.sup.4                                                                          Melting Point                                                                        Elemental Analysis                                    __________________________________________________________________________    304   Cl Cl                                                                              Me Me 198-205° C.                                                                   Analysis       C  H  N                                                        Calcd. for C.sub.13 H.sub.15 Cl.sub.2 N.sub.5                                 O.sub.2 S:     41.49                                                                            3.98                                                                             18.50                                                    Found:         41.27                                                                            3.81                                                                             18.28                            305   CF.sub.3                                                                         H Me Me 74.5-84° C.                                                                   Exact mass calcd for C.sub.14 H.sub.16 F.sub.3                                N.sub.5 O.sub.2 S: 375.0979                                                   Found:             375.0978                           306   Cl Cl                                                                              H  Me 230- 235° C.                                                                  Analysis       C  H  N                                                        Calcd. for C.sub.12 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:     39.89                                                                            3.32                                                                             19.39                                                    Found:         39.72                                                                            3.42                                                                             19.90                            __________________________________________________________________________

The compounds of the present invention are highly effective herbicideswhen applied to the locus of vegetation, herein defined as encompassingpreemergent (soil) applications as well as postmergent (foliar)applications. They have utility for broadspectrum pre- and/orpostemergence weed control in areas where complete vegetation control isdesired. The subject compounds are also useful for selective pre- and/orpostemergence weed control in crops such as wheat. Certain of thesecompounds are effective for the control of nutsedge (cyperus spp.) andsome compounds may be used for selective weed control in corn, soybeansand rice.

For all such uses, unmodified active ingredients of the presentinvention can be employed. However, the present invention embraces theuse of a herbicidally-effective amount of the active ingredients incomposition form with an inert material known in the art as anagricultural adjuvant or carrier in solid or liquid form. Such adjuvantsor carriers must not be phytotoxic to valuable crops particularly at theconcentration employed in applying the composition in attemptingselective weed control in the presence of crops. If weed control isdesired in the absence of crops, it is generally sufficient to employadjuvants or carriers which do not leave a persistent phytotoxicresidue.

Thus, for example, an active ingredient can be dispersed on afinely-divided solid and employed therein as a dust. Also, the activeingredients, as liquid concentrates or solid compositions comprising oneor more of the active ingredients can be dispersed in water, typicallywith aid of a wetting agent, and the resulting aqueous dispersionemployed as a spray. In other procedures the active ingredients can beemployed as a constituent of organic liquid compositions, oil-in-waterand water-in-oil emulsions or dispersions, with or without the additionof wetting, dispersing, or emulsifying agents.

Suitable adjuvants of the foregoing type are well known to those skilledin the art. The methods of applying the solid or liquid herbicidalformulations similarly are well known to the skilled artisan.

Organic solvents that can be employed include toluene, xylene, kerosene,diesel fuel, fuel oil, and petroleum naphtha, ketones such as acetone,methylethyl ketone and cyclohexanone, chlorinated hydrocarbons such astrichloroethylene, and perchloroethylene, esters such as ethyl acetate,amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethylether and diethylene glycol monomethyl ether, alcohols, e.g., methanol,ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol,butylcarbitol acetate and glycerine. Mixtures of water and organicsolvents, either as emulsions or solutions, can be employed.

The active ingredients of the present invention can also be applied asaerosols, e.g., by dispersing them by means of a compressed gas such asone of the fluorocarbons or one of its hydrocarbon successors.

The active ingredients of the present invention can also be applied withsolid adjuvants or carriers such as talc, pyrophyllite, synthetic finesilica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, Fuller's earth, cotton seed hulls, wheatflour, soybean flour, pumice, tripoli, wood flour, walnut shell flour,redwood flour and lignin.

As stated, it is frequently desirable to incorporate a surface-activeagent in the compositions if the present invention. Such surface-activeor wetting agents are advantageously employed in both the solid andliquid compositions. The surface-active agent can be anionic, cationicor nonionic in character.

Typical classes of surface-active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long-chain mercaptans andalkylene oxides. Typical examples of such surface-active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkyl phenol ethylene oxide condensation products, e.g.,p-isooctylphenol condensed with 20 ethylene oxide units, soaps, e.g.,sodium stearate and potassium oleate, sodium salt of propylnaphthalenesulfonic acid, di(2-ethylhexyl)ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decyl sulfonate, sodium salt of thesulfonated monoglyceride of coconut fatty acids, sorbitan sequioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether, polyethylene glycol estersof fatty acids and rosin acids, e.g., Ethofat® 7 and 13, sodiumN-methyl-N-oleyl taurate, sodium dibutylnaphthalene sulfonate, sodiumlignin sulfonate, polyethylene glycol stearate, sodium dodecyl benzenesulfonate, tertiary dodecyl polyethylene glycol thioether (nonionic218), long-chain ethylene oxide-propylene oxide condensation productse.g., Pluronic® 61 (molecular weight about 1000), polyethylene glycolester of tall oil acids, sodium octophenoxyethoxyethyl sulfate,tris(polyoxyethylene)sorbitan monostearate (Tween® 60), and sodiumdihexylsulfosuccinate.

The herbicidally effective concentration of the active ingredients insolid or liquid compositions generally is from about 0.00003 to about 95percent by weight or more. Concentrations from about 0.05 to about 50percent by weight are often employed. In compositions to be employed asconcentrates, the active ingredient can be present in a concentrationfrom about 5 to about 98 weight percent, preferably 15-50 weightpercent. The active ingredient compositions can also contain othercompatible additaments, for example, phytotoxicants, plant growthregulants, pesticides and the like and can be formulated with solidparticulate fertilizer carriers such as ammonium nitrate, urea and thelike.

In further embodiments, the compounds of the present invention orcompositions containing the same, can be advantageously employed incombination with one or more additional pesticidal compounds. Suchadditional pesticidal compounds may be insecticides, nematocides,miticides, arthropodicides, herbicides, fungicides or bactericides thatare compatible with the compounds of the present invention in the mediumselected for application. In such embodiments, the pesticidal compoundis employed as a supplemental toxicant for the same or for a differentpesticidal use or as an additament.

The compounds of the present invention are particularly useful incombination with other herbicides including the substituted ureaherbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea,3-(3,4-dichlorophenyl)-1-methoxy-1methylurea (Lorox®) and1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea (Cotoran®); the triazinessuch as 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine and2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-s-triazine(Bladex®); the uracils such as 5-bromo-3-sec-butyl-6-methyluracil;N-(phosphonomethyl)glycine; the phenoxys such as2,4-dichlorophenoxyacetic acid; picolinic acids such as4-amino-3,5,6-trichloropicolinic acid (Tordon®) and3,6-dichloropicolinic acid (Lontrel®); 4-chloro-2-butynyl-3-chlorophenylcarbamate (Carbyne®); diisopropylthiocarbamic acid, ester with2,3-dichloroallyl alcohol (Avadex®); diisopropylthiocarbamic acid, esterwith 2,3,3-trichloroallyl alcohol (Avadex® BVD);ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (Suffix®);1,2-dimethyl-3,5-diphenylpyrazolium methylsulfate (Avenge®); methyl(2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate) (Hoelon®); butyl2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate(Fusilade®); esters of 2-[4-[(3-chloro-5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propionic acid;4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5-(4H)-one (Lexone®);3-isopropyl-1H-2,1,3-benzothiadiazin-(4)-3H-one 2,2-dioxide;α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine;1,1'-dimethyl-4,4'-bipyridinium ion;2-chloro-2',6'-diethyl-(methoxymethyl)acetanilide; and2-[1-(ethoxyimino)butyl]-5-[(2-ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one(Poast®).

The rates of application for compounds of the invention are determinedby a number of factors including the active ingredient being applied,the particular action desired (e.g., general or selective control), theplant species to be modified and the stage of growth thereof, the partof the plant to be contacted with the toxic active ingredient, theformulation selected, weather and climate, etc. Thus, it is to beunderstood that all of the active ingredients of the present inventionand compositions containing the same may not be equally effective atsimilar concentrations or against the same plant species. Innon-selective preemergence and foliar treatments, the active ingredientsof the invention are usually applied at an approximate rate of fromabout 0.01 to about 10 pounds/acre. In pre- and postemergence operationsfor selective uses, a dosage of about 0.01 to about 10 pounds/acre isgenerally applicable, a rate of 0.01 to 4 pounds/acre being preferred.

The following example illustrates the effect of the compounds of thisinvention applied postemergently.

Plant species in this and other tests were the following:

    ______________________________________                                        Common Name         Scientific Name                                           ______________________________________                                        A.     cotton           Gossypium spp.                                        B.     rape             Brassica napus                                        C.     soybean          Glycine max.                                          D.     sugar beet       Beta saccharifera                                     E.     cocklebur        Xanthium spp.                                         F.     jimsonweed       Datura stramonium                                     G.     annual morning glory                                                                           Ipomoea spp.                                          H.     pigweed          Amaranthus spp.                                       I.     velvetleaf       Abutilon theophrasti                                  J.     corn             Zea mays                                              K.     rice             Oryza sativa                                          L.     sorghum          Sorghum vulgare                                       M.     wheat            Triticum aestivum                                     N.     barnyardgrass    Echinochloa crusgalli                                        (watergrass)                                                           O.     crabgrass        Digitaria spp.                                        P.     yellow foxtail   Setaria lutescens                                     Q.     johnson grass    Sorghum halepense                                     R.     wild oats        Avena fatua                                           S.     sprangletop      Leptochloa filiformis                                 T.     yellow nutsedge  Cyperus esculentus                                    ______________________________________                                    

EXAMPLE 94

In representative operations, each compound to be utilized in a seriesof tests is dissolved in acetone to one-half of the final volume (twicethe final concentration) to be used and the acetone solution in eachcase is admixed with an equal volume of water containing 0.1 percent byweight of surface active material. The compositions, generally in thenature of an emulsion, were employed to spray separate respective plantspecies which had been grown to a 2-4 leaf stage in soil of goodnutrient content in a greenhouse. Sufficient amounts were employed toprovide various application rates as listed in the table. The variousbeds were positioned side by side and exposed to substantially identicalconditions of temperature and light. Each bed was maintained so as toprevent any interaction with test compounds in different seed beds.Other plants were left untreated to serve as controls. After treatment,the plants were maintained for about two weeks under greenhouseconditions conducive for good plant growth and watered as necessary. Thespecific plant species, test compound and dosage and the percentpostermergent control obtained are set forth in the table below. Controlrefers to the reduction in growth compared to the observed results ofthe same untreated species.

    __________________________________________________________________________    POSTEMERGENT CONTROL OF PLANT SPECIES                                         __________________________________________________________________________    Dosage     Plant Species                                                      Compound                                                                            (ppm)                                                                              A  B  C  D  E  F  G  H  I  J                                       __________________________________________________________________________    1     500  0  60 30 85 0  0  0  60 70 0                                       2     1000 10 50 40 90 80 90 10 0  50 0                                       4     500  10 40 40 70 40 60 0  0  60 0                                       6     500  60 80 70 90 90 30 80 30 90 0                                       7     500  -- 90 55 100                                                                              100                                                                              20 90 60 65 0                                       8     500  -- 90 75 95 90 90 70 50 75 20                                            62.5 -- 60 40 60 70 15 35 40 20 0                                       9     1000 50 60 65 80 90 90 20 80 40 0                                       10    2000 15 30 50 75 90 0  0  100                                                                              15 10                                            500  0  10 20 60 15 0  0  20 0  0                                       12    500  -- 100                                                                              80 95 100                                                                              70 100                                                                              100                                                                              95 10                                            125  -- 95 80 95 100                                                                              20 60 90 75 0                                             15.6 -- 75 60 65 90 0  20 70 0  0                                       13    250  95 100                                                                              95 100                                                                              100                                                                              90 90 100                                                                              95 15                                            62.5 95 100                                                                              95 95 100                                                                              50 90 100                                                                              80 0                                             15.6 60 90 85 90 100                                                                              30 85 70 70 0                                       14    1000 20 -- 25 90 80 0  10 60 0  0                                       15    1000 -- 70 25 40 80 0  70 40 60 0                                       17    1000 20 95 15 15 10 0  0  60 85 30                                            500  15 70 15 10 10 0  0  50 70 20                                      19    1000 90 90 90 100                                                                              90 95 40 100                                                                              80 0                                       21    1000 90 100                                                                              70 95 95 0  45 80 30 0                                       22    250  100                                                                              100                                                                              95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              95 25                                            62.5 95 100                                                                              90 100                                                                              100                                                                              95 80 100                                                                              95 15                                            15.6 85 95 90 90 90 80 75 95 90 0                                       24    1500 40 90 40 70 90 -- 0  -- 50 0                                       25    250  100                                                                              100                                                                              90 100                                                                              100                                                                              100                                                                              80 100                                                                              95 70                                            62.5 90 100                                                                              80 100                                                                              100                                                                              100                                                                              35 100                                                                              60 40                                            15.6 30 -- 70 90 90 80 20 100                                                                              40 20                                      26    500  100                                                                              100                                                                              95 100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              80                                            125  100                                                                              100                                                                              85 100                                                                              100                                                                              100                                                                              85 100                                                                              90 80                                            31.25                                                                              90 100                                                                              80 95 90 60 75 100                                                                              40 20                                      30    500  0  40 30 0  40 0  60 0  40 0                                       31    125  90 100                                                                              95 100                                                                              90 100                                                                              60 85 90 40                                            31.25                                                                              75 95 90 90 75 80 40 80 95 50                                            7.8  60 60 75 100                                                                              60 60 0  55 85 30                                      32    500  20 0  15 30 15 60 0  0  50 0                                             250  30 0  15 0  0  30 0  0  40 0                                       33    500  50 60 40 40 60 40 60 10 80 25                                      34    500  70 100                                                                              90 100                                                                              100                                                                              90 75 100                                                                              100                                                                              0                                       35    500  0  70 70 80 95 30 40 90 0  0                                       38    62.5 80 98 90 100                                                                              98 60 80 98 98 0                                             15.6 10 98 70 98 95 50 50 80 40 0                                       39    62.5 98 98 98 98 100                                                                              90 98 100                                                                              98 0                                             15.6 80 98 98 98 95 90 95 95 98 0                                             3.9  40 95 40 98 90 40 70 70 40 0                                       40    1000 25 90 25 90 80 60 20 75 20 0                                       41    4000 30 -- -- -- -- -- 70 -- 98 --                                      43    2000 0  20 15 0  0  0  0  -- 0  0                                       44    250  40 80 75 80 85 20 75 90 80 0                                       45    500  0  70 60 70 25 0  10 -- 50 0                                       46    31.3 95 98 98 98 98 95 98 100                                                                              98 15                                            7.8  80 95 98 98 98 80 98 100                                                                              98 15                                            1.9  60 98 95 95 95 30 90 90 95 15                                      47    62.5 70 90 98 100                                                                              98 20 98 90 98 0                                       48    500  10 75 55 70 70 30 60 -- 40 0                                       49    250  90 100                                                                              95 100                                                                              100                                                                              100                                                                              95 90 100                                                                              0                                             62.5 95 100                                                                              95 100                                                                              100                                                                              100                                                                              95 80 100                                                                              0                                       50    62.5 98 100                                                                              100                                                                              100                                                                              98 98 98 98 100                                                                              93                                            15.6 90 100                                                                              98 90 98 90 80 90 100                                                                              70                                      51    62.5 98 98 98 98 100                                                                              95 98 90 100                                                                              40                                            7.8  30 70 80 95 95 60 90 20 70 0                                       52    2000 70 10 70 50 70 0  -- 0  0  0                                       53    62.5 90 100                                                                              98 100                                                                              100                                                                              98 90 100                                                                              100                                                                              0                                             15.6 60 98 98 98 98 98 90 100                                                                              98 0                                       54    62.5 98 98 98 100                                                                              98 90 98 98 98 30                                            7.8  60 98 80 98 98 40 40 90 50 0                                       55    125  25 70 15 95 80 25 20 20 20 0                                       56    62.5 85 95 90 100                                                                              99 85 80 95 90 0                                       57    125  20 95 10 85 80 0  0  0  -- 0                                       58    125  90 100                                                                              95 100                                                                              100                                                                              95 95 100                                                                              100                                                                              85                                            31.25                                                                              90 100                                                                              95 100                                                                              100                                                                              95 90 100                                                                              95 75                                      59    250  0  70 10 40 75 50 0  0  -- 0                                       60    2000 60 -- 15 -- -- 50 80 100                                                                              80 --                                      61    125  40 75 90 90 30 75 5  60 40 0                                       62    125  40 80 90 70 80 75 65 75 80 0                                       63    62.5 90 90 90 90 95 95 80 90 90 0                                       64    125  100                                                                              99 90 100                                                                              -- 95 80 100                                                                              100                                                                              85                                      65    250  -- 85 75 60 -- 10 0  40 -- 70                                      66    1000 50 80 0  90 -- 0  0  95 30 0                                       67    1000 40 70 0  30 -- 0  0  100                                                                              30 0                                       68    1000 70 80 60 100                                                                              100                                                                              75 50 100                                                                              90 0                                             125  80 50 40 40 60 25 0  65 50 0                                       69    500  90 90 40 100                                                                              -- 90 80 100                                                                              85 90                                            62.5 75 80 5  40 -- 50 60 100                                                                              50 40                                      70    250  90 95 70 90 95 95 80 50 85 0                                       71    500  75 70 35 70 0  60 0  0  70 0                                       72    62.5 100                                                                              100                                                                              85 50 100                                                                              90 85 70 100                                                                              0                                       73    125  0  50 50 30 80 70 20 40 50 0                                       74    500  70 100                                                                              80 100                                                                              100                                                                              90 80 70 100                                                                              0                                       75    125  25 65 40 0  75 40 0  0  100                                                                              0                                       76    125  80 95 90 90 90 100                                                                              90 100                                                                              100                                                                              40                                            31.25                                                                              60 95 80 60 70 50 80 80 98 30                                      77    125  80 100                                                                              90 80 85 100                                                                              95 100                                                                              100                                                                              10                                            15.6 50 -- 75 20 50 80 50 20 80 0                                       78    125  75 95 90 85 40 0  0  100                                                                              90 0                                       79    2000 80 90 70 90 75 85 15 30 75 0                                       81    2000 50 -- 10 0  -- 20 0  30 40 0                                       82    500  85 100                                                                              85 95 85 90 85 100                                                                              85 0                                       83    62.5 50 60 10 60 20 0  0  0  30 0                                       84    2000 30 100                                                                              40 100                                                                              -- -- 0  100                                                                              98 0                                       85    62.5 70 -- 80 100                                                                              70 70 75 100                                                                              80 30                                            7.8  50 -- 80 100                                                                              55 80 55 100                                                                              80 0                                       86    125  50 80 80 100                                                                              60 -- 0  100                                                                              65 0                                       87    250  50 80 75 100                                                                              40 50 40 70 60 0                                       89    2000 50 -- 35 80 70 85 20 100                                                                              90 0                                       90    500  0  70 50 -- 75 70 30 100                                                                              50 0                                       91    62.5 100                                                                              100                                                                              90 100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              0                                       92    62.5 25 50 80 0  -- 90 80 60 50 40                                      93    500  0  70 90 70 80 80 0  70 20 0                                       94    2000 0  60 85 100                                                                              80 70 0  70 70 0                                       97    1000 70 90 70 90 90 20 50 100                                                                              80 0                                       98    4000 60 -- -- -- -- 60 100                                                                              90 -- --                                      99    2000 25 80 60 65 0  0  0  50 20 0                                       101   2000 40 -- 50 100                                                                              50 80 0  100                                                                              35 0                                       103   4000 0  -- -- -- -- -- 100                                                                              100                                                                              80 --                                      104   125  65 95 90 100                                                                              85 100                                                                              100                                                                              100                                                                              100                                                                              100                                           3.9  35 85 80 100                                                                              70 75 90 100                                                                              90 85                                      105   500  35 40 95 90 100                                                                              60 70 60 0  80                                      106   500  30 40 90 0  90 0  80 40 0  90                                            250  0  20 90 0  40 0  80 20 0  50                                      107   1000 0  50 85 15 80 0  0  40 25 0                                       108   500  70 40 75 70 80 30 10 0  90 80                                            125  60 25 75 35 70 15 0  0  20 85                                      111   250  25 90 70 90 95 50 80 70 85 0                                       112   125  0  90 85 90 95 65 80 60 85 0                                       113   250  30 70 15 90 90 50 80 70 75 0                                       114   1000 25 95 40 100                                                                              100                                                                              100                                                                              80 -- 90 0                                             62.5 0  50 25 0  20 60 0  0  60 0                                       116   250  100                                                                              -- 45 100                                                                              95 90 25 95 90 0                                       117   500  90 100                                                                              35 100                                                                              100                                                                              100                                                                              80 75 100                                                                              0                                             62.5 60 75 0  80 90 90 50 40 50 0                                       118   500  0  80 0  100                                                                              100                                                                              100                                                                              70 70 80 0                                       119   500  0  100                                                                              0  50 70 90 30 0  70 30                                      120   4000 100                                                                              -- -- -- -- -- 98 100                                                                              98 --                                      133   4000 20 -- -- -- -- -- 40 100                                                                              40 --                                      135   2000 0  50 40 90 75 75 0  -- 75 0                                       136   500  30 80 30 80 98 30 40 90 70 0                                       137   1000 -- -- 50 100                                                                              70 100                                                                              100                                                                              100                                                                              80 0                                             62.5 40 -- 35 90 30 70 50 100                                                                              75 0                                       138   125  70 100                                                                              40 80 80 80 50 100                                                                              85 0                                             31.2 40 98 0  70 70 50 0  100                                                                              65 0                                       139   125  60 98 50 100                                                                              100                                                                              85 90 100                                                                              100                                                                              0                                       140   125  90 100                                                                              65 100                                                                              100                                                                              95 100                                                                              100                                                                              90 0                                             31.2 95 100                                                                              50 100                                                                              100                                                                              80 50 100                                                                              85 0                                       141   125  60 98 80 100                                                                              70 98 90 100                                                                              98 0                                             31.2 60 100                                                                              75 100                                                                              65 80 80 100                                                                              95 0                                       142   2000 80 75 50 95 100                                                                              80 75 -- 35 0                                       143   62.5 98 100                                                                              60 100                                                                              95 50 100                                                                              100                                                                              0  70                                            15.6 98 98 20 100                                                                              90 20 100                                                                              100                                                                              0  50                                            3.9  80 70 0  98 40 0  60 90 0  0                                       144   62.5 80 95 15 100                                                                              99 99 80 100                                                                              100                                                                              0                                             7.8  55 70 0  100                                                                              85 70 35 95 95 0                                       145   62.5 75 90 35 100                                                                              100                                                                              90 95 100                                                                              100                                                                              0                                             7.8  50 65 0  95 95 55 65 100                                                                              75 0                                       146   62.5 50 95 85 100                                                                              100                                                                              95 95 100                                                                              100                                                                              15                                            3.9  20 50 5  70 90 75 60 75 75 0                                       147   15.6 80 90 45 100                                                                              -- 90 80 100                                                                              100                                                                              0                                             3.9  25 70 5  100                                                                              -- 60 60 90 90 0                                       148   25   75 -- 0  -- -- 80 0  100                                                                              90 --                                      149   2000 0  -- 0  -- -- 0  0  100                                                                              10 --                                      150   125  10 70 0  90 90 90 35 70 80 0                                       151   62.5 95 100                                                                              25 -- 100                                                                              100                                                                              95 100                                                                              95 0                                             15.6 80 75 0  -- 100                                                                              100                                                                              90 100                                                                              95 0                                       152   125  100                                                                              100                                                                              45 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0                                             7.8  90 90 0  90 80 80 85 90 100                                                                              0                                       153   125  90 100                                                                              35 100                                                                              100                                                                              100                                                                              85 100                                                                              100                                                                              0                                             7.8  70 100                                                                              0  100                                                                              60 70 55 40 90 0                                       154   62.5 40 90 0  80 95 90 50 20 90 0                                       155   125  90 100                                                                              20 100                                                                              100                                                                              95 85 100                                                                              100                                                                              0                                             15.6 75 90 0  95 50 80 15 80 95 0                                       156   31.25                                                                              75 90 0  100                                                                              90 100                                                                              85 100                                                                              100                                                                              0                                       157   15.6 70 90 0  80 50 90 40 70 90 0                                       158   31.25                                                                              75 95 20 100                                                                              40 90 60 90 95 0                                             7.8  45 80 10 90 0  80 10 40 65 0                                       159   125  100                                                                              100                                                                              25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0                                             15.6 50 100                                                                              0  100                                                                              70 100                                                                              70 70 95 0                                       160   62.5 65 80 65 100                                                                              75 -- 60 100                                                                              100                                                                              0                                       161   250  80 85 40 80 65 100                                                                              75 100                                                                              60 15                                      162   62.5 40 80 0  -- 10 70 20 95 80 0                                       163   500  0  70 0  0  40 70 0  90 20 0                                       164   125  90 95 30 100                                                                              80 95 80 100                                                                              100                                                                              0                                             31.25                                                                              60 90 0  100                                                                              50 50 10 100                                                                              90 0                                       165   62.5 70 70 30 90 50 50 60 100                                                                              80 0                                             15.6 45 40 0  70 20 50 40 80 45 0                                       166   62.5 60 65 55 70 70 60 75 100                                                                              90 80                                            15.6 40 40 40 60 20 50 50 100                                                                              80 0                                       168   62.5 60 -- 80 -- 70 70 98 100                                                                              90 0                                             15.6 20 90 80 -- 50 -- 75 100                                                                              60 0                                       169   125  50 80 0  80 30 70 0  70 65 0                                       170   500  50 -- 30 95 25 90 70 100                                                                              90 25                                            125  50 100                                                                              0  90 15 80 60 100                                                                              80 0                                       171   2000 60 30 -- 90 0  50 0  0  50 0                                       172   1000 40 80 50 80 20 70 20 100                                                                              70 0                                       173   125  0  80 40 100                                                                              0  -- 0  80 0  0                                       174   62.5 80 -- 70 90 80 85 100                                                                              100                                                                              100                                                                              20                                            7.8  100                                                                              80 50 90 40 80 70 100                                                                              90 0                                       175   62.5 100                                                                              -- 40 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0                                       176   250  0  95 65 80 0  80 50 100                                                                              80 0                                       177   62.5 90 98 80 90 98 85 80 100                                                                              100                                                                              50                                            7.8  50 85 60 80 50 40 80 100                                                                              100                                                                              0                                       178   250  50 90 50 80 90 85 35 -- 80 0                                       179   62.5 0  50 10 75 50 15 0  0  0  0                                       180   500  100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              0                                             125  95 100                                                                              90 100                                                                              100                                                                              100                                                                              90 -- 100                                                                              0                                       181   125  90 99 95 90 80 -- 80 100                                                                              95 0                                       182   125  90 98 95 -- 100                                                                              98 60 100                                                                              98 0                                       183   125  65 95 0  98 50 90 0  95 90 0                                       184   125  95 100                                                                              90 -- 90 100                                                                              85 100                                                                              100                                                                              0                                       185   62.5 90 98 -- 95 90 90 50 -- 90 0                                       186   4000 100                                                                              -- -- -- -- -- 80 100                                                                              100                                                                              --                                      187   125  40 -- 90 85 80 80 80 98 90 0                                       188   125  90 80 95 85 60 80 100                                                                              100                                                                              90 0                                       189   125  80 100                                                                              85 100                                                                              25 80 80 90 90 0                                       190   125  98 80 85 100                                                                              80 -- 20 100                                                                              85 15                                      191   125  60 100                                                                              80 95 70 100                                                                              80 98 98 0                                             31.2 40 100                                                                              80 80 20 80 80 50 70 0                                       192   125  80 100                                                                              20 100                                                                              -- 90 90 100                                                                              90 0                                             31.25                                                                              40 90 0  100                                                                              -- 80 40 100                                                                              20 0                                       193   250  80 100                                                                              40 100                                                                              30 100                                                                              80 100                                                                              98 0                                       194   250  50 100                                                                              60 100                                                                              70 100                                                                              10 100                                                                              95 0                                       195   250  80 90 65 100                                                                              25 85 80 98 100                                                                              0                                       196   250  70 100                                                                              40 100                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              0                                       197   250  80 85 40 80 65 100                                                                              75 100                                                                              60 15                                      198   2000 60 100                                                                              0  90 0  0  50 30 90 0                                       199   62.5 40 100                                                                              90 90 -- 40 10 98 80 0                                       200   62.5 0  95 35 95 -- 30 0  40 50 0                                       201   500  0  20 0  50 80 70 0  90 60 0                                       204   1000 70 60 15 60 -- 50 0  0  90 0                                       205   250  -- 75 60 95 -- 60 40 100                                                                              -- 45                                      206   250  40 100                                                                              20 100                                                                              100                                                                              90 98 100                                                                              98 0                                       207   1000 90 100                                                                              25 100                                                                              95 95 50 30 100                                                                              0                                       208   62.5 80 100                                                                              65 95 65 95 50 100                                                                              90 0                                       209   250  0  70 0  40 80 70 0  0  70 0                                       210   62.5 35 30 20 40 0  -- 0  0  55 0                                       211   1000 20 -- 0  40 20 -- 0  75 60 0                                       212   2000 0  -- 55 98 50 -- 0  100                                                                              70 0                                       213   125  95 100                                                                              90 100                                                                              70 100                                                                              80 100                                                                              100                                                                              98                                            31.2 90 30 80 100                                                                              50 80 70 100                                                                              98 98                                      214   62.5 75 -- 90 100                                                                              70 -- 50 100                                                                              -- 90                                      215   62.5 80 -- 90 80 70 80 50 100                                                                              98 90                                      216   62.5 80 -- 85 100                                                                              70 80 95 100                                                                              80 90                                      217   31.2 0  -- 75 -- 40 60 70 100                                                                              85 80                                      218   62.5 20 -- 90 -- 40 80 80 100                                                                              85 0                                       219   62.5 80 -- 90 98 60 -- 80 100                                                                              90 90                                            15.6 65 -- 80 90 35 -- 40 100                                                                              90 0                                       220   62.5 -- 50 80 -- 45 50 50 100                                                                              85 90                                      221   62.5 -- -- 50 -- 60 80 80 100                                                                              -- 75                                      222   62.5 -- -- 80 -- 30 100                                                                              80 100                                                                              -- 75                                      223   125  65 98 80 100                                                                              60 100                                                                              100                                                                              100                                                                              100                                                                              100                                           15.6 50 90 80 80 40 100                                                                              90 100                                                                              90 98                                      227   250  0  -- 0  -- 80 70 80 100                                                                              50 40                                            31.2 0  -- 0  20 50 50 50 100                                                                              0  0                                       228   125  0  50 0  80 90 50 0  100                                                                              40 20                                      229   125  30 100                                                                              80 100                                                                              100                                                                              60 70 100                                                                              98 0                                             31.2 0  98 70 75 98 40 50 100                                                                              75 0                                       230   125  0  70 50 80 70 80 35 100                                                                              85 80                                      231   125  25 98 65 100                                                                              80 100                                                                              100                                                                              100                                                                              85 100                                           31.2 0  90 50 100                                                                              70 80 80 100                                                                              50 95                                      232   4000 50 -- -- -- -- -- 10 0  50 --                                      233   250  0  80 40 0  20 30 -- 50 50 0                                       234   4000 60 -- -- -- -- -- 0  100                                                                              0  --                                      235   1000 20 70 30 50 70 70 20 100                                                                              -- 90                                      236   1000 0  -- 60 80 75 80 70 100                                                                              70 0                                       237   1000 50 70 80 30 70 -- 50 100                                                                              80 75                                      239   4000 90 -- -- -- -- -- 98 100                                                                              90 --                                      240   2000 -- -- 50 100                                                                              20 60 30 100                                                                              80 20                                      241   2000 0  -- 30 50 0  0  20 98 30 0                                       242   2000 0  -- 0  70 40 0  0  0  70 0                                       243   500  80 100                                                                              85 95 100                                                                              95 80 80 90 75                                            31.25                                                                              70 90 80 90 100                                                                              80 70 40 80 0                                       244   500  100                                                                              100                                                                              45 100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              40                                            125  90 100                                                                              30 100                                                                              100                                                                              90 80 85 100                                                                              0                                       245   4000 0  -- -- -- -- -- 50 0  30 --                                      246   500  80 70 85 100                                                                              90 80 50 100                                                                              70 0                                       247   500  0  70 70 70 20 20 0  70 40 0                                       248   500  50 100                                                                              40 75 0  0  0  0  100                                                                              0                                       250   500  0  70 50 30 50 50 25 40 70 0                                       255   2000 20 50 5  80 70 0  10 40 0  0                                       257   4000 0  -- -- -- -- -- 20 100                                                                              60 --                                      258   4000 0  -- -- -- -- -- 20 -- 20 --                                      260   500  80 95 90 100                                                                              -- 95 40 45 90 0                                       261   500  60 95 90 90 -- 95 90 65 95 0                                       262   500  100                                                                              100                                                                              95 100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              50                                            31.25                                                                              80 100                                                                              90 100                                                                              -- 100                                                                              90 100                                                                              95 0                                       263   500  50 100                                                                              0  100                                                                              -- 80 80 90 40 0                                       264   250  0  50 70 80 -- 80 80 50 0  0                                       265   500  0  60 40 80 -- 0  60 70 0  0                                       266   500  10 75 80 30 -- 90 85 25 75 0                                       267   500  0  80 45 80 -- 80 90 60 95 0                                       268   31.25                                                                              100                                                                              100                                                                              10 -- 95 80 90 100                                                                              100                                                                              0                                       269   62.5 80 90 0  100                                                                              0  80 90 30 100                                                                              0                                       270   62.5 70 80 10 100                                                                              60 -- 55 100                                                                              70 35                                            3.9  45 70 0  55 20 75 20 60 55 0                                       271   1000 65 80 40 100                                                                              50 -- 60 100                                                                              80 0                                             62.5 50 70 0  60 0  -- 0  20 60 0                                       272   62.5 45 60 0  80 30 50 0  50 70 0                                       273   500  -- 100                                                                              40 100                                                                              40 100                                                                              80 100                                                                              50 0                                       274   2000 80 90 46 100                                                                              75 80 80 100                                                                              100                                                                              50                                      275   125  -- -- 0  -- 80 98 60 100                                                                              -- 60                                      276   125  -- -- 0  -- 70 100                                                                              65 100                                                                              -- 80                                      277   125  0  -- 50 -- 60 80 20 100                                                                              -- 75                                            31.2 0  -- 20 -- 0  80 0  100                                                                              -- 0                                       278   125  -- -- 30 -- 60 70 60 100                                                                              -- 0                                       279   125  -- -- 20 -- 70 98 60 100                                                                              -- 0                                       280   250  -- -- 0  -- 60 -- 60 100                                                                              -- 75                                      281   125  -- -- 0  -- 60 100                                                                              60 100                                                                              -- --                                      282   125  70 80 50 80 70 80 80 100                                                                              80 0                                             31.2 60 80 20 -- 50 70 50 100                                                                              85 0                                       283   125  50 80 80 80 70 100                                                                              80 100                                                                              80 0                                       284   125  -- -- 0  -- 70 100                                                                              80 100                                                                              -- 20                                      285   125  80 90 70 90 70 100                                                                              50 100                                                                              98 0                                             7.8  -- 80 0  80 50 100                                                                              40 100                                                                              80 0                                       286   125  30 100                                                                              65 80 30 90 80 100                                                                              80 0                                       287   125  70 80 70 85 40 80 70 100                                                                              80 0                                       288   125  30 95 70 90 40 -- 80 100                                                                              90 0                                       289   1000 50 98 55 90 70 100                                                                              80 100                                                                              80 0                                       290   125  30 80 50 85 40 100                                                                              80 100                                                                              80 0                                       291   125  40 85 40 85 60 100                                                                              30 100                                                                              80 0                                             7.8  20 60 0  85 0  50 30 100                                                                              60 0                                       292   125  60 100                                                                              50 -- 90 80 80 100                                                                              100                                                                              35                                            31.2 40 95 0  -- 60 70 80 100                                                                              95 0                                       293   125  90 100                                                                              30 100                                                                              90 80 0  100                                                                              98 0                                             31.2 50 80 10 80 90 50 0  100                                                                              85 0                                       294   125  60 98 55 85 98 90 70 100                                                                              98 0                                       297   125  70 100                                                                              50 -- 80 80 0  100                                                                              95 0                                       298   2000 35 95 30 80 90 80 50 100                                                                              85 0                                             500  35 85 0  80 50 50 50 100                                                                              80 0                                       299   2000 0  50 0  80 0  0  40 100                                                                              50 0                                       300   125  60 98 15 85 70 85 60 100                                                                              85 0                                             62.5 50 98 0  80 50 85 50 100                                                                              85 0                                       301   2000 30 90 15 85 60 -- 50 100                                                                              90 0                                       304   62.5 90 95 80 -- 95 95 85 100                                                                              90 0                                       305   250  90 98 98 98 98 90 70 100                                                                              100                                                                              0                                       306   125  50 -- 98 90 -- -- 80 100                                                                              90 0                                       __________________________________________________________________________    Dosage     Plant Species                                                      Compound                                                                            (ppm)                                                                              K  L   M  N  O   P  Q  R   T                                       __________________________________________________________________________    1     500  0  40  0  15 0   40 60 0   0                                       2     1000 20 0   0  0  0   0  90 0   0                                       4     500  40 40  0  0  20  0  80 0   0                                       6     500  20 80  0  35 20  0  80 0   90                                      7     500  15 65  0  35 0   25 50 0   65                                      8     500  40 70  10 70 10  25 90 0   60                                            62.5 30 20  0  5  0   10 20 0   0                                       9     1000 30 90  0  20 40  0  30 0   40                                      10    2000 -- 10  0  0  0   0  0  0   60                                            500  -- 0   0  0  0   0  0  0   0                                       12    500  25 75  0  80 25  20 55 0   90                                            125  10 60  0  10 0   0  25 0   40                                            15.6 0  0   0  0  0   0  0  0   0                                       13    250  15 90  0  90 20  70 90 0   90                                            62.5 0  80  0  100                                                                              0   50 85 0   75                                            15.6 0  80  0  0  0   0  70 0   0                                       14    1000 30 0   0  0  0   0  0  0   0                                       15    1000 35 40  0  0  0   0  0  0   10                                      17    1000 0  60  10 0  15  10 85 0   0                                             500  0  40  0  0  0   20 60 0   0                                       19    1000 0  50  0  20 20  0  65 0   85                                      21    1000 20 30  0  0  0   0  20 0   80                                      22    250  50 90  10 100                                                                              90  100                                                                              100                                                                              20  85                                            62.5 20 90  0  100                                                                              75  90 100                                                                              0   80                                            15.6 0  75  0  100                                                                              0   95 85 0   40                                      24    1500 20 10  0  0  --  -- 10 0   0                                       25    250  60 85  0  90 90  95 100                                                                              20  80                                            62.5 10 80  0  70 70  90 90 0   60                                            15.6 0  60  0  20 0   70 75 0   0                                       26    500  80 90  30 100                                                                              90  90 100                                                                              0   90                                            125  40 85  0  100                                                                              80  75 95 0   80                                            31.25                                                                              0  50  0  100                                                                              20  30 60 0   80                                      30    500  20 0   0  0  0   0  0  0   0                                       31    125  0  90  0  40 80  90 100                                                                              0   75                                            31.25                                                                              0  80  0  20 75  80 100                                                                              0   80                                            7.8  0  50  0  0  0   60 80 0   50                                      32    500  10 0   30 0  10  10 95 0   0                                             250  20 0   0  0  0   0  80 0   0                                       33    500  0  80  0  0  0   0  60 0   10                                      34    500  0  60  0  0  0   0  20 0   60                                      35    500  0  20  -- 0  0   0  0  0   0                                       38    62.5 0  20  0  10 10  95 90 0   30                                            15.6 0  0   0  0  5   80 50 0   10                                      39    62.5 0  65  0  50 70  97 90 0   40                                            15.6 0  80  0  40 0   90 80 0   20                                            3.9  0  5   0  0  0   80 0  0   0                                       40    1000 0  20  0  0  0   0  0  0   20                                      41    4000 -- --  -- 80 40  40 -- --  95                                      43    2000 0  0   0  0  25  0  20 0   0                                       44    250  0  20  0  0  0   40 0  0   60                                      45    500  50 0   0  0  0   0  0  0   0                                       46    31.3 0  0   0  0  10  80 50 0   40                                            7.8  0  0   0  0  0   0  0  0   20                                            1.9  0  0   0  0  0   0  0  0   10                                      47    62.5 0  0   0  0  0   0  0  0   10                                      48    500  0  0   0  0  0   0  0  0   0                                       49    250  10 80  0  90 80  95 80 20  90                                            62.5 0  70  0  80 60  90 100                                                                              0   90                                      50    62.5 97 90  0  95 95  99 97 90  90                                            15.6 97 50  0  80 80  97 95 10  80                                      51    62.5 40 90  0  20 0   93 95 10  80                                            7.8  0  50  0  0  0   0  20 0   70                                      52    2000 0  0   0  0  0   0  0  0   0                                       53    62.5 10 90  0  70 50  95 97 0   60                                            15.6 0  90  0  65 20  97 93 0   80                                      54    62.5 40 93  20 50 30  95 97 15  30                                            7.8  0  25  0  0  0   25 60 0   0                                       55    125  0  0   0  0  0   0  0  0   0                                       56    62.5 0  55  0  0  40  75 95 0   15                                      57    125  0  70  -- 0  0   0  85 0   0                                       58    125  60 95  60 95 90  90 100                                                                              --  90                                            31.25                                                                              50 90  0  90 95  90 95 --  90                                      59    250  0  0   0  0  0   0  0  0   0                                       60    2000 0  10  0  -- 0   0  -- --  15                                      61    125  15 0   0  0  70  25 35 0   5                                       62    125  15 45  0  0  10  10 80 0   15                                      63    62.5 10 60  0  50 40  65 60 0   60                                      64    125  70 80  80 0  90  80 90 0   80                                      65    250  0  70  0  50 70  90 90 0   15                                      66    1000 0  20  0  0  30  0  80 0   0                                       67    1000 0  0   0  0  20  20 0  0   0                                       68    1000 25 80  0  30 80  95 75 0   75                                            125  0  25  0  0  0   50 60 0   20                                      69    500  0  80  0  80 80  90 95 0   80                                            62.5 0  40  0  0  0   70 30 0   60                                      70    250  0  0   0  0  75  80 80 0   90                                      71    500  0  0   0  0  20  0  0  0   0                                       72    62.5 35 50  0  50 0   40 70 0   85                                      73    125  0  0   0  0  0   0  0  0   25                                      74    500  0  80  0  70 0   60 50 0   95                                      75    125  20 0   0  10 0   0  0  0   5                                       76    125  80 40  20 35 65  98 60 10  95                                            31.25                                                                              70 50  0  30 50  85 30 0   80                                      77    125  30 0   0  40 20  98 20 0   15                                            15.6 15 0   0  0  0   40 20 0   15                                      78    125  50 50  0  10 10  50 0  0   75                                      79    2000 0  75  0  10 0   0  60 25  0                                       81    2000 0  0   0  0  0   0  0  0   40                                      82    500  0  0   0  0  0   0  0  0   0                                       83    62.5 0  0   0  0  0   0  0  0   0                                       84    2000 0  0   0  0  0   0  0  0   30                                      85    62.5 0  40  0  50 50  75 0  0   60                                            7.8  0  20  0  0  0   70 0  0   50                                      86    125  0  40  0  30 0   70 0  0   20                                      87    250  0  20  0  0  0   0  0  20  30                                      89    2000 10 30  0  0  50  40 0  0   50                                      90    500  0  0   0  0  --  70 20 0   0                                       91    62.5 0  0   0  0  0   95 20 0   95                                      92    62.5 0  0   0  0  0   0  0  0   0                                       93    500  0  0   0  0  0   0  0  0   15                                      94    2000 0  25  0  20 0   0  0  0   80                                      97    1000 30 55  0  60 0   70 60 0   0                                       98    4000 -- --  -- 0  30  98 -- 0   0                                       99    2000 20 0   0  0  0   0  0  0   0                                       101   2000 30 0   0  20 0   80 0  0   50                                      103   4000 -- --  -- 0  0   0  -- 0   --                                      104   125  100                                                                              100 80 100                                                                              100 100                                                                              100                                                                              80  80                                            3.9  85 95  50 100                                                                              --  100                                                                              95 50  60                                      105   500  20 0   0  20 0   -- 0  0   0                                       106   500  30 40  20 30 0   0  90 30  0                                             250  10 30  0  0  0   0  80 20  0                                       107   1000 0  40  0  0  0   0  75 0   0                                       108   500  0  80  60 100                                                                              0   0  100                                                                              0   35                                            125  0  90  0  100                                                                              0   0  80 0   5                                       111   250  0  10  0  0  0   0  50 0   60                                      112   125  0  60  0  0  0   0  15 0   40                                      113   250  0  50  0  0  0   0  10 0   60                                      114   1000 0  25  85 90 0   40 30 0   75                                            62.5 0  0   0  0  0   0  0  0   0                                       116   250  0  0   0  10 0   65 0  0   50                                      117   500  0  60  0  0  0   65 75 0   25                                            62.5 0  15  0  0  0   40 25 0   0                                       118   500  0  0   -- 0  60  20 0  0   70                                      119   500  0  0   0  0  0   0  80 0   40                                      120   4000 -- --  -- 90 70  98 -- 50  --                                      133   4000 -- --  -- 0  0   0  -- 0   0                                       135   2000 0  10  0  0  0   0  0  0   0                                       136   500  0  0   0  0  0   0  0  0   0                                       137   1000 50 50  25 75 98  80 80 50  50                                            62.5 30 0   0  60 20  75 20 0   20                                      138   125  80 50  30 80 60  85 70 0   0                                             31.2 0  0   0  20 0   85 70 0   0                                       139   125  0  65  20 0  20  75 80 0   40                                      140   125  100                                                                              95  30 80 80  80 100                                                                              50  35                                            31.2 55 70  0  20 50  98 90 0   0                                       141   125  80 65  50 80 95  100                                                                              80 70  80                                            31.2 80 55  0  75 0   80 80 0   60                                      142   2000 0  75  0  0  50  80 80 0   0                                       143   62.5 93 0   93 60 97  97 97 0   90                                            15.6 30 0   35 50 80  80 80 0   70                                            3.9  0  0   0  10 70  70 0  0   0                                       144   62.5 75 80  0  80 100 95 100                                                                              0   85                                            7.8  15 25  0  50 40  90 10 0   55                                      145   62.5 -- 80  0  15 25  75 75 0   20                                            7.8  -- 45  0  0  0   0  65 0   0                                       146   62.5 90 75  0  95 95  95 90 --  85                                            3.9  40 10  0  20 0   75 25 --  55                                      147   15.6 0  0   0  0  20  80 40 0   80                                            3.9  0  0   0  0  0   0  0  0   15                                      148   25   -- 70  0  -- 60  95 -- --  90                                      149   2000 -- 0   0  -- 0   90 -- --  0                                       150   125  0  0   0  10 0   80 25 0   65                                      151   62.5 25 40  0  80 0   85 -- 0   95                                            15.6 0  0   0  30 0   85 -- 0   90                                      152   125  50 80  0  100                                                                              0   100                                                                              90 0   95                                            7.8  0  40  0  55 0   90 65 0   90                                      153   125  50 80  0  90 25  100                                                                              80 0   90                                            7.8  0  20  0  70 0   55 0  0   80                                      154   62.5 25 0   0  0  0   0  0  0   30                                      155   125  20 75  10 15 0   75 75 0   95                                            15.6 0  15  0  0  0   50 10 0   80                                      156   31.25                                                                              40 20  0  0  0   0  10 0   85                                      157   15.6 0  80  0  0  0   75 80 0   0                                       158   31.25                                                                              0  50  0  10 0   70 50 0   0                                             7.8  0  0   0  0  0   25 0  0   0                                       159   125  35 75  -- 100                                                                              0   75 100                                                                              0   90                                            15.6 15 50  -- 50 0   60 40 0   10                                      160   62.5 0  50  0  30 50  70 30 0   100                                     161   250  0  65  0  15 30  50 10 0   50                                      162   62.5 40 55  0  15 30  70 0  0   0                                       163   500  0  0   0  0  0   50 0  0   0                                       164   125  0  85  0  65 0   70 75 0   70                                            31.25                                                                              0  15  0  0  0   60 0  0   85                                      165   62.5 0  0   0  50 0   70 20 0   80                                            15.6 0  0   0  20 0   50 25 0   60                                      166   62.5 0  0   0  80 80  85 100                                                                              30  70                                            15.6 0  0   0  65 0   50 0  0   60                                      168   62.5 0  0   0  0  90  80 -- 0   80                                            15.6 0  0   0  0  0   75 -- 0   --                                      169   125  0  20  0  0  0   0  0  0   0                                       170   500  35 25  0  75 60  80 85 80  98                                            125  30 50  0  40 60  70 80 40  --                                      171   2000 -- 0   0  0  --  0  0  0   0                                       172   1000 0  0   0  0  0   40 0  0   50                                      173   125  25 0   -- 0  --  20 50 0   0                                       174   62.5 70 70  25 80 98  80 85 85  90                                            7.8  30 20  0  40 20  80 40 40  100                                     175   62.5 30 80  0  100                                                                              100 100                                                                              80 40  20                                      176   250  0  20  0  0  0   20 100                                                                              0   0                                       177   62.5 98 90  50 100                                                                              80  98 98 60  65                                            7.8  80 50  0  80 50  95 80 20  45                                      178   250  75 0   0  0  0   0  0  0   0                                       179   62.5 0  0   0  0  0   0  0  0   0                                       180   500  10 50  0  10 90  75 20 0   90                                            125  0  40  0  0  40  60 0  0   40                                      181   125  0  50  0  0  0   95 40 0   0                                       182   125  0  0   0  0  20  95 20 30  20                                      183   125  0  20  0  0  20  20 20 0   0                                       184   125  0  50  0  0  20  80 30 100 50                                      185   62.5 -- 50  0  0  --  -- 20 0   0                                       186   4000 -- --  -- 50 70  90 -- 30  90                                      187   125  0  0   0  0  0   70 0  0   70                                      188   125  50 50  20 70 80  80 60 70  70                                      189   125  25 50  0  70 50  70 40 25  70                                      190   125  0  40  0  0  20  85 40 0   0                                       191   125  80 70  30 100                                                                              60  100                                                                              90 65  30                                            31.2 50 70  0  75 20  100                                                                              80 50  30                                      192   125  0  0   0  0  0   40 0  0   98                                            31.25                                                                              0  0   0  0  0   0  0  0   90                                      193   250  20 0   0  60 60  90 75 0   65                                      194   250  0  10  0  0  30  80 25 0   70                                      195   250  0  0   0  20 20  80 30 0   60                                      196   250  0  30  10 20 70  80 40 10  70                                      197   250  0  65  0  15 30  50 10 0   50                                      198   2000 0  0   0  0  0   0  0  0   0                                       199   62.5 0  0   0  0  0   0  0  0   0                                       200   62.5 0  0   0  0  0   0  0  0   35                                      201   500  0  0   0  0  0   0  0  0   0                                       204   1000 0  10  0  0  0   0  0  0   10                                      205   250  0  80  0  40 95  95 100                                                                              0   60                                      206   250  0  0   0  0  20  90 80 0   80                                      207   1000 0  0   0  20 0   20 40 0   70                                      208   62.5 0  15  0  0  0   50 0  0   25                                      209   250  0  0   0  0  0   0  0  0   0                                       210   62.5 0  0   0  0  0   0  0  0   0                                       211   1000 0  10  0  0  0   0  25 0   0                                       212   2000 0  50  0  0  0   0  0  --  0                                       213   125  20 85  0  70 90  100                                                                              100                                                                              50  65                                            31.2 0  85  0  35 90  100                                                                              98 30  50                                      214   62.5 35 100 70 80 20  100                                                                              98 50  80                                      215   62.5 30 85  20 90 80  85 100                                                                              40  65                                      216   62.5 0  50  40 80 80  80 80 50  70                                      217   31.2 30 70  0  80 100 60 75 0   35                                      218   62.5 0  30  0  0  80  25 0  0   0                                       219   62.5 0  60  25 60 70  85 85 0   --                                            15.6 0  50  0  0  50  70 70 0   0                                       220   62.5 55 30  0  80 90  85 60 70  0                                       221   62.5 0  --  0  50 80  75 90 0   70                                      222   62.5 0  --  0  0  0   50 50 0   70                                      223   125  70 100 100                                                                              100                                                                              100 100                                                                              100                                                                              80  70                                            15.6 80 100 80 98 45  100                                                                              100                                                                              70  55                                      227   250  30 25  0  0  0   80 50 40  50                                            31.2 0  20  0  0  0   40 30 0   0                                       228   125  0  0   0  0  80  0  60 0   0                                       229   125  -- 0   -- 0  20  70 50 0   20                                            31.2 50 0   0  0  0   50 0  0   20                                      230   125  0  55  0  0  0   55 70 0   50                                      231   125  90 100 90 100                                                                              100 100                                                                              100                                                                              60  75                                            31.2 80 75  70 80 50  100                                                                              95 40  70                                      232   4000 -- --  -- 0  0   0  -- 0   80                                      233   250  20 0   0  0  0   0  0  0   0                                       234   4000 -- --  -- 0  0   0  -- --  20                                      235   1000 20 35  25 75 98  45 75 60  0                                       236   1000 20 0   0  50 70  80 25 50  70                                      237   1000 50 45  40 40 0   80 85 65  0                                       239   4000 -- --  -- 20 20  50 -- 30  90                                      240   2000 0  20  0  25 70  80 50 0   65                                      241   2000 0  0   0  0  75  75 0  0   70                                      242   2000 20 0   0  0  15  0  0  --  0                                       243   500  45 75  20 70 0   75 80 0   95                                            31.25                                                                              0  70  0  0  0   0  30 0   95                                      244   500  40 90  20 40 40  95 80 0   90                                            125  0  80  0  0  0   80 65 0   80                                      245   4000 -- --  -- 0  0   0  -- 0   0                                       246   500  70 95  0  50 75  90 75 0   80                                      247   500  0  0   0  0  0   0  0  0   0                                       248   500  50 80  0  0  0   0  0  0   0                                       250   500  0  0   0  0  0   0  0  0   0                                       255   2000 0  0   0  0  0   0  0  0   0                                       257   4000 -- --  -- 0  0   0  -- 0   0                                       258   4000 -- --  -- 0  0   0  -- 0   0                                       260   500  0  25  0  50 0   90 95 0   0                                       261   500  0  30  0  20 10  95 100                                                                              0   0                                       262   500  40 90  10 100                                                                              95  100                                                                              100                                                                              0   80                                            31.25                                                                              0  75  0  80 65  95 100                                                                              0   15                                      263   500  85 70  0  40 90  95 100                                                                              0   0                                       264   250  0  20  0  20 0   60 10 0   0                                       265   500  0  0   0  0  0   0  0  0   0                                       266   500  40 0   0  75 70  80 0  0   0                                       267   500  40 65  0  35 90  70 75 0   40                                      268   31.25                                                                              10 75  0  100                                                                              0   85 0  0   95                                      269   62.5 0  50  0  30 0   0  70 0   0                                       270   62.5 0  50  0  60 70  70 0  40  50                                            3.9  0  10  0  20 0   65 0  0   0                                       271   1000 0  50  0  85 80  90 30 0   50                                            62.5 0  35  0  30 0   0  0  0   45                                      272   62.5 0  0   0  20 20  50 0  0   20                                      273   500  20 40  0  20 100 75 30 0   40                                      274   2000 70 100 0  100                                                                              98  98 80 0   80                                      275   125  0  --  0  20 100 90 80 30  60                                      276   125  0  --  40 90 90  80 90 0   70                                      277   125  80 --  20 25 70  80 -- 0   25                                            31.2 20 --  0  0  0   100                                                                              -- 0   0                                       278   125  0  --  0  70 100 90 -- 0   80                                      279   125  35 --  0  60 90  80 -- 0   80                                      280   250  0  --  -- 70 95  90 -- 0   50                                      281   125  0  --  0  70 85  98 -- 0   70                                      282   125  30 70  0  80 100 80 100                                                                              0   75                                            31.2 0  50  0  80 70  75 98 0   20                                      283   125  50 80  0  80 90  80 90 0   25                                      284   125  0  --  0  75 80  85 90 30  70                                      285   125  60 50  0  80 80  85 100                                                                              0   60                                            7.8  0  20  0  0  0   75 70 0   0                                       286   125  80 50  0  80 90  85 90 0   60                                      287   125  0  35  0  20 80  80 80 0   0                                       288   125  30 50  0  70 100 80 80 50  30                                      289   1000 35 80  0  80 90  85 80 0   0                                       290   125  50 50  0  80 100 70 80 50  25                                      291   125  20 50  0  80 95  80 85 0   20                                            7.8  0  0   0  0  0   20 20 0   0                                       292   125  70 50  0  80 65  98 100                                                                              50  60                                            31.2 60 40  0  20 20  98 75 --  20                                      293   125  60 80  0  70 80  100                                                                              80 50  0                                             31.2 30 50  0  20 50  95 50 20  0                                       294   125  50 50  0  90 85  98 90 0   0                                       297   125  50 80  0  50 80  95 100                                                                              20  0                                       298   2000 50 60  20 70 65  98 60 40  20                                            500  40 40  0  65 25  75 50 --  0                                       299   2000 0  0   0  0  0   0  50 0   0                                       300   125  30 20  0  70 75  85 70 0   0                                             62.5 30 50  0  65 50  50 70 0   0                                       301   2000 0  25  0  30 70  100                                                                              50 0   0                                       304   62.5 40 20  0  50 55  90 -- 0   60                                      305   250  90 95  0  25 15  90 97 0   40                                      306   125  60 60  0  30 80  98 50 0   70                                      __________________________________________________________________________

So as to clearly illustrate the phytotoxic properties of the variousactive ingredients of the present invention applied preemergently, acontrolled greenhouse experiment is described below.

EXAMPLE 95

The seeds of various species of plants were planted in beds of goodagricultural soil in a greenhouse. A number of compositions of thepresent invention, generally in the nature of an aqueous emulsion, wereapplied at rates listed in the table so as to deposit a predeterminedamount of active ingredients uniformly throughout the surface of thebed. Another seed bed was treated only with water to serve as a control.After treatment the seed beds were maintained for two weeks undergreenhouse conditions conducive for good plant growth and watered asnecessary. The specific plant species, test compound, and dosage and thepercent preemergent control are set forth in the table below. Controlrefers to the reduction in growth compared to the observed results ofthe same untreated species.

    __________________________________________________________________________    PREEMERGENT CONTROL OF PLANT SPECIES                                              Dosage                                                                    Com-                                                                              (lb/-                                                                              Plant Species                                                        pound                                                                             acre A  B  C  D  F  G  H  I  J  K  L  M  N  O  Q  R  P  T                 __________________________________________________________________________    1   10   90 -- -- -- -- 90 100                                                                              98 -- -- -- -- 100                                                                              100                                                                              -- 90 100                                                                              --                2   0.5  0  95 30 70 0  100                                                                              30 95 15 20 60 0  80 95 50 30 95  0                4   10   98 -- -- -- -- 90 100                                                                              90 -- -- -- -- 100                                                                              80 -- 90 100 --               6   0.5  100                                                                              100                                                                              95 95 0  30 70 60 10 90 50 50 90 70 10 -- 50  40                   0.25 70 100                                                                              10 95 0  0  100                                                                              60 0  80 50 0  80 0  0  -- --  50               7   1.0  95 98 95 98 100                                                                              80 100                                                                              95 90 98 95 100                                                                              98 80 80 20 70  90                   0.125                                                                              20 98 20 90 0  40 50 40 0  70 70 0  30 0  10 0  20  0                8   1.0  100                                                                              100                                                                              95 100                                                                              100                                                                              60 100                                                                              90 95 100                                                                              -- 55 95 95 95 70 95  95                   0.25 90 100                                                                              95 90 100                                                                              25 95 60 80 90 -- 0  75 70 80 15 60  75               9   0.5  0  100                                                                              40 100                                                                              100                                                                              0  30 0  0  50 20 0  98 40 0  -- 20  0                10  1.0  0  98 0  90 0  0  95 75 0  80 -- 0  0  40 0  0  0   0                12  0.25 95 95 95 98 0  50 60 30 50 10 -- 0  40 10 80 0  0   50                   0.125                                                                              80 95 40 95 0  0  0  20 0  0  -- 0  10 0  50 0  0   30               13  0.25 95 98 95 98 70 90 95 95 80 95 98 20 95 80 95 10 90  98                   0.062                                                                              90 98 80 90 50 90 20 95 0  60 95 0  50 0  90 0  50  80               14  4.0  90 95 20 99 10 0  90 10 10 10 15 0  10 95 60 20 0   0                15  1.0  90 95 60 70 0  30 30 80 10 15 -- 0  10 15 20 0  10  5                16  1.0  100                                                                              0  15 0  0  15 35 0  15 20 -- 0  0  0  0  0  0   0                17  1.0  0  90 0  40 0  0  70 0  10 50 10 0  0  0  0  0  0   0                19  1.0  95 98 95 95 80 80 98 85 35 50 60 0  40 70 30 80 60  90                   0.25 90 95 20 90 0  50 90 70 0  20 0  0  0  20 0  0  0   40               21  2.0  80 95 70 98 70 60 100                                                                              75 50 80 -- 0  0  60 40 0  0   60               22  0.25 95 100                                                                              95 98 100                                                                              70 100                                                                              98 50 90 95 50 95 95 98 90 98  98                   0.062                                                                              80 100                                                                              95 95 100                                                                              30 80 80 0  10 60 0  40 90 40 90 95  90               24  10   95 -- -- -- -- 80 100                                                                              98 -- -- -- -- 70 70 -- 10 70  --               25  0.25 98 100                                                                              98 100                                                                              98 80 100                                                                              98 100                                                                              100                                                                              -- 70 98 100                                                                              98 95 100 95                   0.062                                                                              95 98 95 95 70 40 0  70 98 95 -- 0  60 20 90 0  50  50               26  0.25 95 98 98 100                                                                              100                                                                              95 100                                                                              95 100                                                                              100                                                                              -- 0  98 100                                                                              98 40 100 100                  0.062                                                                              95 98 95 98 95 80 100                                                                              90 95 90 -- 0  30 95 60 0  60  100              29  10   90 -- -- -- -- 0  60 0  -- -- -- -- 0  20 20 0  --  --               30  1.0  0  0  95 0  100                                                                              0  100                                                                              0  0  0  0  0  0  90 0  90 30  0                31  0.25 80 98 95 100                                                                              100                                                                              65 100                                                                              95 95 95 98 50 98 100                                                                              100                                                                              100                                                                              98  100                  0.062                                                                              70 60 90 90 100                                                                              0  95 90 0  10 50 0  98 95 90 0  98  80               32  0.5  50 100                                                                              90 100                                                                              100                                                                              98 95 100                                                                              20 60 40 40 100                                                                              98 100                                                                              100                                                                              98  50                   0.125                                                                              20 0  60 50 40 30 95 90 0  0  50 0  30 95 65 0  0   0                33  1.0  90 98 90 50 95 60 95 80 95 95 70 80 98 98 95 40 98  98                   0.25 20 80 10 50 40 0  0  10 0  0  0  0  70 50 10 0  40  0                34  1.0  95 100                                                                              95 95 95 80 98 95 60 70 80 0  70 20 95 30 40  90                   0.25 80 95 80 90 0  20 50 80 0  40 90 0  20 0  80 0  0   70               35  2.0  60 80 60 98 0  10 -- 50 0  0  0  0  0  60 80 0  0   40               36  1.0  0  30 0  50 100                                                                              0  0  0  0  0  0  0  0  0  0  0  0   0                37  0.25 95 95 95 97 100                                                                              90 100                                                                              95 95 97 95 0  97 70 95 0  97  100                  0.062                                                                              95 93 35 100                                                                              40 30 100                                                                              90 20 50 30 0  30 0  50 0  20  97               39  0.25 95 95 95 97 100                                                                              90 100                                                                              95 95 97 95 0  97 70 95 0  97  100                  0.031                                                                              90 93 30 97 0  30 100                                                                              50 0  0  0  0  0  0  0  0  0   60               40  4    20 100                                                                              50 60 100                                                                              0  -- 20 0  50 -- 0  0  -- 0  0  0   70               41  0.25 40 80 25 80 0  10 0  10 0  0  20 0  80 10 35 0  30  70               42  16   0  100                                                                              100                                                                              70 0  0  -- 30 0  0  -- 0  0  -- 0  100                                                                              0   0                43  4.0  30 40 20 95 0  60 70 30 0  0  0  0  20 40 40 0  0   0                44  0.25 85 93 80 97 100                                                                              20 95 0  10 70 93 70 40 90 80 40 70  90               46  0.125                                                                              95 95 97 97 100                                                                              90 100                                                                              97 60 0  50 60 70 97 10 60 95  99                   0.031                                                                              95 95 93 97 100                                                                              70 100                                                                              80 0  0  0  0  0  70 0  0  30  97               47  2.0  97 97 97 100                                                                              97 70 99 99 0  0  0  30 -- 40 20 30 --  97                   0.5  50 90 85 97 90 20 99 90 0  0  0  0  -- 40 10 0  --  90               49  0.062                                                                              100                                                                              100                                                                              100                                                                              99 100                                                                              99 -- 90 90 10 -- 0  85 -- 50 0  90  100              48  1.0  30 20 0  50 60 60 0  0  0  0  0  20 20 10 0  70 20  0                50  0.25 80 95 95 100                                                                              100                                                                              80 100                                                                              93 99 97 100                                                                              100                                                                              95 25 95 60 95  99                   0.062                                                                              0  93 85 97 75 40 80 90 90 100                                                                              80 0  97 0  90 10 93  99               51  0.25 93 95 90 95 95 80 100                                                                              95 97 80 97 97 97 95 95 100                                                                              97  100                  0.062                                                                              50 95 10 93 90 70 70 20 45 10 55 0  0  90 10 0  45  80               52  2.0  30 80 -- 30 0  50 0  35 0  0  0  0  0  25 0  0  0   10               53  0.125                                                                              90 95 90 100                                                                              97 85 100                                                                              90 97 97 97 30 95 95 93 99 93  100                  0.031                                                                              20 93 20 100                                                                              85 40 95 0  20 80 15 0  10 80 75 0  60  97               54  0.125                                                                              95 93 95 97 99 70 100                                                                              90 95 99 97 0  93 95 95 40 95  97                   0.031                                                                              85 93 35 97 90 0  100                                                                              20 0  93 50 0  15 10 40 0  45  55               56  0.25 0  100                                                                              0  100                                                                              0  90 -- 50 30 0  -- 0  0  -- 0  0  20  70               57  4    100                                                                              100                                                                              100                                                                              100                                                                              0  0  -- 0  40 0  -- 0  20 -- 80 0  50  0                58  0.062                                                                              0  100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              70 0  -- 0  30 -- 80 50 90  100              59  20   0  100                                                                              60 100                                                                              90 35 -- 50 0  0  -- 0  0  -- 0  0  0   0                60  0.5  0  50 20 0  0  100                                                                              -- 0  50 0  -- 0  0  -- 0  40 0   0                61  5    100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 70 85 100                                                                              -- 0  65 -- 90 0  100 90               62  0.5  0  90 50 50 0  0  -- 20 0  80 -- 0  20 -- 0  0  20  60               63  0.125                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  -- 100                                                                              30 90 -- 40 10 -- 0  0  30  100              64  0.062                                                                              50 100                                                                              100                                                                              90 100                                                                              70 -- 90 60 0  30 0  0  -- 40 0  90  90               65  0.25 0  20 100                                                                              100                                                                              90 50 -- 20 0  30 -- 0  70 -- 95 0  95  95               66  10   100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 80 100                                                                              -- 50 100 --               67  10   30 -- -- -- -- 100                                                                              30 30 -- -- -- -- 70 -- -- 40 --  --               68  1    100                                                                              100                                                                              80 90 100                                                                              0  -- 90 80 0  90 20 70 -- 50 20 80  50               69  0.5  100                                                                              100                                                                              50 100                                                                              0  30 -- 40 93 0  100                                                                              70 0  -- 20 0  70  100              70  1    90 100                                                                              70 95 100                                                                              30 -- 80 100                                                                              40 90 80 40 -- 90 60 90  95               71  10   98 -- -- -- -- 50 100                                                                              70 -- -- -- -- 50 98 -- 70 100 --               72  0.25 40 100                                                                              90 90 100                                                                              10 -- 60 90 70 80 90 30 -- 50 90 50  100              73  0.125                                                                              0  30 0  0  0  0  0  0  0  0  40 0  0  0  0  0  0   0                74  0.125                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              0  -- 70 0  0  100                                                                              0  30 -- 70 0  70  100              75  0.5  0  100                                                                              0  90 0  20 -- 90 0  0  0  -- 20 -- 0  0  80  0                76  0.25 60 100                                                                              95 100                                                                              100                                                                              90 -- 100                                                                              100                                                                              70 90 100                                                                              70 -- 80 90 90  100              77  0.25 0  80 80 50 90 60 -- 0  70 40 50 0  20 -- 0  0  80  90               78  0.25 0  100                                                                              30 70 0  0  -- 30 10 40 0  40 20 -- 0  30 20  50               79  0.5  40 100                                                                              40 70 90 10 -- 30 50 30 10 0  0  -- 0  -- 0   0                80  10   0  -- -- -- -- -- 100                                                                              80 -- -- -- -- 0  0  -- -- 0   --               82  0.125                                                                              0  90 0  90 0  0  0  0  0  0  0  0  0  0  0  0  0   0                83  0.5  0  98 0  30 50 0  -- 20 0  0  0  0  0  0  0  0  0   0                84  10   30 -- -- -- -- 20 90 98 -- -- -- -- 0  0  -- 0  0   --               85  0.125                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              70 0  0  0  20 -- 30 0  60  100                  0.015                                                                              70 100                                                                              30 -- 90 20 -- 60 0  0  0  0  0  -- 0  0  0   0                86  0.25 0  100                                                                              20 100                                                                              100                                                                              0  -- 0  0  0  0  0  0  -- 0  0  0   0                87  4    80 90 65 -- 20 70 -- 0  0  0  70 0  0  -- 50 0  40  100              90  2    100                                                                              100                                                                              70 100                                                                              100                                                                              70 -- 95 80 90 70 20 50 -- 40 30 80  90                   1    90 100                                                                              50 100                                                                              60 30 -- 30 70 20 40 0  0  -- 30 0  80  100              91  0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              40 -- 100                                                                              60 30 50 0  20 -- 40 0  70  100                  0.062                                                                              20 100                                                                              90 90 100                                                                              0  -- 50 0  0  20 0  0  -- 0  0  20  20               92  0.5  10 100                                                                              0  70 -- 0  -- 0  0  0  40 0  0  -- 0  0  0   0                93  0.5  70 40 20 0  0  0  -- 0  0  10 0  -- 0  -- 0  0  0   0                94  0.25 60 100                                                                              50 0  0  0  -- 0  0  0  0  -- 0  -- 0  0  0   0                97  1.0  30 100                                                                              0  20 80 0  -- 0  0  0  10 40 0  -- 0  0  0   100              98  10   80 -- -- -- -- 40 100                                                                              98 -- -- -- -- 90 90 -- 40 90  --               101 10   40 -- -- -- -- 0  40 70 -- -- -- -- 0  60 -- 20 0   --               104 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100 100                  0.016                                                                              100                                                                              100                                                                              80 100                                                                              80 100                                                                              -- 100                                                                              95 95 100                                                                              100                                                                              100                                                                              -- 100                                                                              90 95  100              106 1    95 95 95 100                                                                              100                                                                              85 -- 98 98 70 98 98 70 20 95 98 70  80               108 0.5  95 95 100                                                                              80 80 70 80 98 95 100                                                                              70 98 85 95 98 50 50  90                   0.125                                                                              40 95 30 70 70 50 40 90 60 80 10 30 0  0  50 0  0   60               110 2.0  0  50 0  0  0  0  -- 0  90 40 50 0  80 0  0  0  0   0                111 0.25 20 95 10 90 95 20 50 80 35 65 65 0  15 90 75 0  30  93               112 0.25 80 85 0  99 0  80 90 20 50 25 20 0  0  97 30 90 0   90               113 0.25 30 90 0  100                                                                              0  0  100                                                                              60 0  40 0  0  20 90 50 0  50  50               114 0.5  95 95 15 50 100                                                                              50 100                                                                              60 0  80 40 0  0  0  10 0  10  80               116 0.5  90 100                                                                              10 100                                                                              100                                                                              20 -- 60 0  0  0  -- 0  -- 0  0  0   30               117 0.5  90 100                                                                              20 90 90 20 -- 90 0  0  0  0  0  -- 60 0  40  0                118 0.5  30 90 0  60 0  0  -- 0  0  0  0  -- 0  -- 0  0  0   0                119 0.5  90 100                                                                              0  90 100                                                                              0  -- 20 0  0  50 0  0  -- 0  0  0   70               120 10   100                                                                              -- -- -- -- 60 100                                                                              98 -- -- -- -- 100                                                                              90 -- 60 90  --               128 1.0  20 100                                                                              0  90 100                                                                              0  -- 30 0  0  50 0  0  -- 0  0  0   0                136 1.0  30 65 0  0  0  0  -- 98 0  0  0  -- 0  0  80 -- 0   10               137 0.25 80 -- 0  100                                                                              10 70 -- 80 0  50 30 30 20 -- 20 -- 20  100              138 0.25 100                                                                              100                                                                              50 90 20 20 -- 90 30 50 50 10 0  -- 90 -- 90  80               139 0.25 100                                                                              100                                                                              50 100                                                                              100                                                                              90 -- 100                                                                              70 90 100                                                                              80 80 -- 100                                                                              -- 100 100              140 0.125                                                                              100                                                                              100                                                                              50 100                                                                              60 80 -- 90 0  -- 70 10 70 -- 70 0  80  100              141 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              95 95 -- 100                                                                              -- 100 75               142 0.5  20 20 0  100                                                                              100                                                                              0  100                                                                              40 0  0  50 0  0  0  0  0  0   25               143 0.25 100                                                                              95 70 100                                                                              100                                                                              90 100                                                                              97 95 97 99 50 97 100                                                                              100                                                                              50 97  100                  0.062                                                                              95 95 25 100                                                                              100                                                                              80 100                                                                              95 60 80 99 0  97 50 85 0  95  100                  0.016                                                                              95 95 25 100                                                                              40 0  40 90 0  70 20 0  75 0  75 0  50  75               144 0.25 100                                                                              100                                                                              60 100                                                                              100                                                                              95 -- 100                                                                              70 40 -- 0  80 -- 100                                                                              70 100 100                  0.062                                                                              100                                                                              90 70 100                                                                              100                                                                              0  -- 60 0  0  -- 0  60 -- 60 0  93  80               145 0.125                                                                              100                                                                              100                                                                              40 100                                                                              100                                                                              60 -- 100                                                                              0  0  -- 0  0  -- 50 0  20  80                   0.062                                                                              90 90 0  100                                                                              50 100                                                                              -- 90 0  0  -- 0  0  -- 20 0  0   40               146 0.125                                                                              100                                                                              85 0  100                                                                              -- 90 -- 90 60 60 -- 0  100                                                                              -- 97 0  95  100                  0.062                                                                              60 30 0  90 -- 0  -- 20 0  30 -- 0  95 -- 90 0  85  100              147 0.031                                                                              70 100                                                                              0  100                                                                              100                                                                              20 -- 100                                                                              20 20 0  30 0  -- 0  90 0   100              148 0.125                                                                              30 90 0  100                                                                              100                                                                              0  -- 50 20 0  -- 0  30 -- 90 0  70  100              149 10   30 -- -- -- -- 40 40 50 -- -- -- -- 50 50 -- 20 20  --               150 0.5  90 100                                                                              30 90 100                                                                              80 -- 20 80 0  95 50 30 -- 70 50 80  95               151 0.031                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              30 -- 90 30 30 40 50 60 -- 50 30 60  100              152 0.031                                                                              90 100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              0  0  40 0  40 -- 30 0  90  100              153 0.031                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              20 -- 100                                                                              30 20 20 0  65 -- 30 0  70  100              154 0.125                                                                              30 100                                                                              0  90 100                                                                              0  -- 20 0  0  10 0  0  -- 0  0  0   100              156 0.125                                                                              90 100                                                                              0  100                                                                              100                                                                              70 -- 90 0  50 90 0  60 -- 20 30 20  95               157 0.031                                                                              100                                                                              100                                                                              0  100                                                                              90 50 -- 100                                                                              0  20 50 0  10 -- 90 0  80  30               158 0.031                                                                              90 100                                                                              0  100                                                                              80 20 -- 100                                                                              0  20 30 0  40 -- 0  0  30  0                159 0.062                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              50 90 70 0  80 -- 80 0  75  70               160 0.62 100                                                                              100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              35 0  60 0  0  -- 0  0  30  100                  0.015                                                                              90 100                                                                              0  100                                                                              100                                                                              80 -- 80 0  0  0  0  0  -- 0  0  0   100              161 10   100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               162 0.125                                                                              80 100                                                                              10 100                                                                              0  0  -- 90 0  0  50 0  40 -- 30 30 80  100              163 2    100                                                                              100                                                                              0  100                                                                              100                                                                              0  -- 60 40 0  0  0  0  -- 0  0  0   60               164 0.125                                                                              90 100                                                                              10 100                                                                              100                                                                              20 -- 100                                                                              0  0  20 0  0  -- 0  0  60  90                   0.031                                                                              70 100                                                                              0  90 70 0  -- 100                                                                              0  0  0  0  0  -- 0  0  20  90               165 0.25 90 75 10 90 90 60 -- 30 0  0  60 0  60 -- 0  0  90  90               166 0.25 100                                                                              100                                                                              80 100                                                                              90 95 -- 100                                                                              10 40 80 20 80 -- 20 30 80  100                  0.062                                                                              80 90 40 100                                                                              70 0  -- 90 0  0  0  0  70 -- 0  0  50  100              169 10   90 -- -- -- -- 100                                                                              100                                                                              98 -- -- -- -- 50 40 -- -- 50  --               170 0.25 70 100                                                                              0  90 0  30 -- 85 20 30 80 10 40 -- 90 -- 70  0                171 0.25 70 100                                                                              20 100                                                                              20 50 -- 90 40 90 100                                                                              50 100                                                                              -- 100                                                                              -- 100 80               172 0.25 100                                                                              -- 90 100                                                                              100                                                                              90 -- 100                                                                              80 100                                                                              100                                                                              90 100                                                                              -- 90 -- 100 100                  0.31 80 -- 0  100                                                                              40 80 -- 90 20 0  90 60 0  -- 70 0  0   100              173 0.25 50 80 0  90 0  0  -- 0  30 70 30 20 30 -- 70 -- 50  0                175 0.125                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.016                                                                              70 100                                                                              0  100                                                                              60 0  -- 60 0  0  30 0  50 -- 50 0  80  70               178 0.25 65 80 0  95 0  10 60 40 0  0  0  -- 25 0  0  -- 0   0                181 0.25 98 100                                                                              80 98 98 80 -- 98 0  30 95 0  20 -- 60 40 80  50               182 0.12 98 98 98 98 99 98 -- 98 0  0  20 0  0  -- 70 0  90  100              183 0.5  98 98 0  100                                                                              98 0  -- 100                                                                              0  0  90 0  0  -- 0  0  0   0                184 0.25 100                                                                              98 50 100                                                                              98 80 -- 100                                                                              0  0  95 0  0  -- 30 0  80  80               185 0.25 98 100                                                                              70 98 90 80 -- 100                                                                              0  20 90 0  20 -- 90 0  --  0                186 0.062                                                                              90 98 20 90 90 0  -- 95 0  0  30 0  30 -- 40 0  50  30               187 10   100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               188 10   98 -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               189 0.25 100                                                                              100                                                                              80 100                                                                              80 50 -- 100                                                                              80 90 100                                                                              80 80 -- 70 -- 80  100                  0.063                                                                              80 100                                                                              60 80 0  50 0  70 0  10 10 50 70 -- 50 -- 40  100              190 0.25 90 -- 90 100                                                                              90 50 -- 50 10 20 95 20 30 -- 30 -- 70  100              191 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              95 -- 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100              192 0.25 95 100                                                                              90 100                                                                              100                                                                              97 -- 100                                                                              10 0  -- 0  0  -- 0  0  70  90               193 0.125                                                                              90 100                                                                              0  100                                                                              100                                                                              40 -- 60 0  0  0  0  0  -- 20 0  0   0                194 0.25 90 100                                                                              70 100                                                                              95 90 -- 90 0  0  30 0  0  -- 0  0  0   95               195 0.125                                                                              30 100                                                                              0  95 100                                                                              60 -- 70 10 0  0  0  0  -- 0  0  20  100              196 0.125                                                                              95 100                                                                              0  95 100                                                                              60 -- 70 0  0  0  0  0  -- 0  0  0   20               197 0.125                                                                              99 99 30 99 99 80 -- 99 0  40 20 10 50 -- 80 10 98  90               198 4    90 100                                                                              0  100                                                                              0  0  -- 80 10 70 20 50 0  -- 0  70 0   30               199 0.25 20 100                                                                              70 90 0  20 -- 70 0  0  -- -- -- -- 0  0  0   0                200 0.5  100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              60 -- 90 50 0  10 0  0  -- 0  0  0   60               202 4    0  20 40 100                                                                              0  100                                                                              -- 0  0  0  -- 0  0  -- 0  0  0   0                203 1.0  40 100                                                                              0  80 0  0  -- 0  0  0  0  0  0  -- 0  0  0   0                204 0.25 80 40 0  90 -- 0  -- 0  40 0  60 0  0  -- 0  0  0   0                205 0.25 100                                                                              100                                                                              90 100                                                                              100                                                                              75 -- 100                                                                              95 50 -- 0  50 -- 0  50 0   70               206 0.5  100                                                                              100                                                                              100                                                                              100                                                                              50 35 -- 100                                                                              0  0  -- 0  40 -- 40 0  60  97               208 0.25 100                                                                              100                                                                              45 100                                                                              90 40 -- 90 0  0  30 0  0  -- 0  0  0   60               209 10   100                                                                              -- -- -- -- 100                                                                              100                                                                              90 -- -- -- -- 70 100                                                                              -- 70 50  --               211 10   90 -- -- -- -- 80 80 95 -- -- -- -- -- 80 -- 50 90  --               212 1    30 30 70 90 30 0  -- 40 10 0  0  0  0  -- 0  0  0   0                213 0.125                                                                              100                                                                              -- 70 100                                                                              90 80 -- 100                                                                              100                                                                              10 100                                                                              70 80 -- 80 50 100 --                   0.031                                                                              50 -- 0  60 90 50 -- 100                                                                              10 0  50 0  0  -- 50 0  0   --               214 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100 100                  0.031                                                                              100                                                                              100                                                                              50 100                                                                              100                                                                              70 -- 100                                                                              90 80 100                                                                              100                                                                              70 -- 90 100                                                                              100 70               215 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100 100                  0.031                                                                              70 100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              70 60 100                                                                              50 10 -- 90 50 90  95               216 0.25 100                                                                              20 70 100                                                                              100                                                                              90 -- 100                                                                              100                                                                              90 100                                                                              100                                                                              75 -- 100                                                                              100                                                                              100 70                   0.063                                                                              50 0  10 70 100                                                                              50 -- 70 50 50 50 100                                                                              70 -- 70 90 100 70               217 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              50 90 100                                                                              100                                                                              90 -- 100                                                                              -- 50  70                   0.125                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              0  0  100                                                                              50 30 -- 90 -- 30  70               218 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              0  0  95 0  0  -- 50 -- 50  50               219 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              50 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.031                                                                              100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              70 10 70 100                                                                              0  -- 100                                                                              -- 70  70               220 0.25 100                                                                              100                                                                              90 100                                                                              100                                                                              70 -- 100                                                                              100                                                                              50 100                                                                              100                                                                              90 -- 100                                                                              -- 100 100                  0.063                                                                              50 80 0  100                                                                              90 30 -- 100                                                                              50 50 10 100                                                                              90 -- 90 -- 100 50               221 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90 100                                                                              100                                                                              90 100                                                                              -- 70 -- 100 100                  0.031                                                                              70 60 0  70 75 90 -- 100                                                                              0  0  30 0  90 -- 0  -- 50  70               222 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              40 90 50 0  0  -- 100                                                                              -- 30  50                   0.125                                                                              100                                                                              100                                                                              60 100                                                                              100                                                                              90 -- 100                                                                              0  100                                                                              30 0  0  -- 70 -- 30  50               213 0.25 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              95 100                                                                              100                                                                              100                                                                              -- 100                                                                              80 100 100                  0.031                                                                              95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90 100                                                                              100                                                                              90 100                                                                              -- 100                                                                              80 75  75               227 0.25 60 100                                                                              0  100                                                                              100                                                                              70 -- 30 40 50 100                                                                              90 50 -- 70 -- 90  100              228 0.25 90 80 20 100                                                                              100                                                                              70 -- 90 50 -- 100                                                                              50 90 -- 90 -- 50  50               229 0.25 100                                                                              100                                                                              30 100                                                                              90 100                                                                              -- 90 40 10 90 0  0  -- 0  -- 0   100              230 0.25 100                                                                              90 20 100                                                                              100                                                                              90 -- 90 90 50 100                                                                              30 100                                                                              -- 90 -- 80  100                  0.063                                                                              80 30 0  100                                                                              100                                                                              30 -- 90 40 50 70 30 0  -- 70 -- 30  50               231 0.063                                                                              100                                                                              100                                                                              20 100                                                                              100                                                                              100                                                                              -- 75 100                                                                              -- 100                                                                              80 95 -- 100                                                                              50 95  90               232 10   90 -- -- -- -- 80 98 98 -- -- -- -- 40 90 -- 40 98  --               233 1    80 100                                                                              20 80 90 70 -- 70 0  0  0  0  0  -- 0  0  0   0                234 2    80 100                                                                              0  0  40 0  -- 0  10 0  30 0  0  -- 30 0  0   100              235 0.25 50 -- 0  50 50 90 -- 20 50 10 50 50 -- -- 0  -- 20  0                236 10   100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               237 0.25 50 -- 40 50 10 20 -- 0  20 20 20 100                                                                              10 -- 10 -- 30  30               238 10   0  -- -- -- -- 0  80 60 -- -- -- -- 0  0  -- 0  0   --               239 10   90 -- -- -- -- 100                                                                              100                                                                              100                                                                              -- -- -- -- 95 98 -- 98 98  --               243 0.125                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              80 -- 60 75 0  90 0  70 -- 80 0  80  100              244 0.125                                                                              70 100                                                                              20 100                                                                              100                                                                              0  -- 100                                                                              0  0  0  0  0  -- 0  0  0   95               245 10   0  -- -- -- -- 100                                                                              0  60 -- -- -- -- 0  0  -- 0  0   --               246 0.25 80 80 90 90 0  0  -- 30 20 20 95 10 0  -- 20 40 20  20               247 2.0  80 100                                                                              100                                                                              100                                                                              100                                                                              0  -- 80 85 70 80 70 60 -- 90 90 70  30               250 0.5  0  100                                                                              0  30 0  10 -- 0  0  0  50 40 10 -- 30 100                                                                              0   0                252 10   0  100                                                                              100                                                                              100                                                                              100                                                                              50 -- 0  80 100                                                                              -- 30 60 -- 50 50 80  90               255 4.0  60 90 15 80 40 0  95 0  0  10 30 0  0  0  40 60 0   15               257 10   90 -- -- -- -- 80 100                                                                              90 -- -- -- -- 0  30 -- 0  30  0                258 2.0  0  10 20 0  100                                                                              0  90 20 0  30 0  0  0  60 0  0  0   0                260 1.0  20 80 0  80 90 50 -- 70 0  0  -- 0  0  -- 40 0  30  70               261 2.0  0  100                                                                              100                                                                              90 -- 90 -- 80 0  0  -- 0  0  -- 10 70 50  0                262 0.25 90 100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              80 95 -- 0  90 -- 60 50 95  100              263 0.5  0  40 0  100                                                                              0  50 -- 20 0  0  -- 0  0  -- 0  50 50  0                264 2.0  0  60 0  40 100                                                                              0  -- 0  10 0  -- 0  0  -- 0  0  0   0                265 10   0  -- -- -- -- 60 60 30 -- -- -- -- 0  0  -- 0  0   --               266 4.0  50 100                                                                              50 90 80 0  -- 0  0  0  30 40 0  -- 0  50 90  80               267 4.0  0  100                                                                              30 80 90 0  -- 90 70 30 30 50 20 -- 10 50 90  0                268 0.25 100                                                                              100                                                                              0  100                                                                              100                                                                              90 -- 100                                                                              80 100                                                                              100                                                                              -- 90 -- 80 30 100 100                  0.015                                                                              70 100                                                                              0  90 90 0  -- 20 0  0  60 0  40 -- 40 0  60  97               269 0.062                                                                              100                                                                              100                                                                              0  90 90 0  -- 90 0  0  70 0  20 -- 10 0  70  90               270 2.0  100                                                                              100                                                                              0  100                                                                              100                                                                              95 -- 98 90 100                                                                              98 70 98 -- 98 80 100 100                  0.125                                                                              98 98 0  98 100                                                                              90 -- 98 30 70 90 0  95 -- 90 20 95  100              272 0.5  90 100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              50 40 50 0  75 -- 60 0  95  100                  0.25 80 100                                                                              0  100                                                                              90 40 -- 100                                                                              0  30 40 0  60 -- 40 0  90  100              273 10   98 -- -- -- -- 98 100                                                                              98 -- -- -- -- 95 98 -- 90 100 --               274 2    100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80 95 100                                                                              30 90 -- 80 20 100 100                  0.25 95 100                                                                              0  100                                                                              90 80 -- 100                                                                              60 80 90 0  80 -- 70 0  95  100              275 0.25 100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80 90 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                              80 100                                                                              0  95 50 50 -- 100                                                                              30 0  60 20 50 -- 90 -- 90  0                276 0.25 80 100                                                                              10 100                                                                              100                                                                              90 -- 100                                                                              60 90 100                                                                              80 100                                                                              -- 90 -- 100 100                  0.063                                                                              70 100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              0  10 90 50 70 -- 80 -- 90  100              277 0.25 50 100                                                                              20 100                                                                              100                                                                              30 -- 40 80 90 80 90 -- 100                                                                              -- 100                                                                              100                  278 0.25 100                                                                              100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              60 90 100                                                                              70 100                                                                              -- 90 -- 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              60 100                                                                              -- 100                                                                              0  50 70 30 50 -- 90 -- 80  100              279 0.25 90 100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80 100                                                                              100                                                                              90 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              90 -- 100                                                                              0  40 90 60 50 -- 80 -- 100 100              280 0.25 80 100                                                                              10 100                                                                              100                                                                              90 -- 100                                                                              50 50 100                                                                              60 100                                                                              -- 90 -- 100 100                  0.063                                                                              80 100                                                                              0  100                                                                              100                                                                              70 -- 100                                                                              10 50 50 90 50 -- 80 -- 100 100              282 0.25 100                                                                              100                                                                              50 100                                                                              100                                                                              80 -- 100                                                                              95 100                                                                              100                                                                              70 70 -- 100                                                                              100                                                                              100 100                  0.063                                                                              100                                                                              100                                                                              10 100                                                                              70 80 -- 100                                                                              0  50 90 50 70 -- 100                                                                              100                                                                              80  70               283 0.25 100                                                                              100                                                                              20 100                                                                              95 80 -- 100                                                                              40 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              70 70 -- 100                                                                              0  80 90 50 85 -- 90 -- 70  90               284 0.25 100                                                                              100                                                                              20 100                                                                              100                                                                              80 -- 100                                                                              85 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90 100 100                  0.063                                                                              70 100                                                                              0  100                                                                              85 70 -- 100                                                                              0  70 90 50 100                                                                              -- 70 10 70  100              286 0.25 100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              50 100                                                                              100                                                                              70 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              100                                                                              -- 100                                                                              0  95 30 0  95 -- 80 -- 100 85               287 0.25 100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              60 100                                                                              100                                                                              70 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              50 -- 100                                                                              0  80 70 100                                                                              100                                                                              -- 80 -- 100 70               288 0.25 100                                                                              100                                                                              40 100                                                                              100                                                                              100                                                                              -- 100                                                                              80 100                                                                              100                                                                              60 100                                                                              -- 100                                                                              90 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              50 100                                                                              -- 100                                                                              0  100                                                                              95 0  75 -- 100                                                                              80 100 60               289 0.25 100                                                                              100                                                                              50 100                                                                              100                                                                              100                                                                              -- 100                                                                              95 -- 100                                                                              80 100                                                                              -- 100                                                                              100                                                                              100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              80 70 -- 100                                                                              60 -- 95 50 60 -- 95 50 100 50               290 0.25 100                                                                              100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              90 100                                                                              100                                                                              95 100                                                                              -- 100                                                                              70 100 80                   0.063                                                                              100                                                                              100                                                                              20 100                                                                              100                                                                              40 -- 100                                                                              60 50 100                                                                              20 70 -- 100                                                                              20 90  50               291 0.25 100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              55 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              70 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              0  -- 100                                                                              0  70 100                                                                              30 75 -- 100                                                                              70 90  100              293 0.25 100                                                                              100                                                                              10 100                                                                              100                                                                              70 -- 100                                                                              60 90 100                                                                              60 100                                                                              -- 95 95 100 100                  0.063                                                                              100                                                                              75 0  100                                                                              95 20 -- 80 0  100                                                                              60 0  20 -- 50 50 65  0                297 0.025                                                                              100                                                                              100                                                                              50 100                                                                              100                                                                              95 -- 100                                                                              80 100                                                                              100                                                                              60 100                                                                              -- 100                                                                              80 100 100                  0.063                                                                              100                                                                              100                                                                              0  100                                                                              90 85 -- 100                                                                              0  50 90 20 65 -- 70 50 40  90               298 0.25 100                                                                              100                                                                              0  100                                                                              100                                                                              70 -- 100                                                                              40 95 95 50 100                                                                              -- 95 50 100 100                  0.063                                                                              90 100                                                                              0  85 0  0  -- 70 0  50 60 20 50 -- 75 20 20  40               304 0.125                                                                              100                                                                              97 90 100                                                                              95 40 100                                                                              95 90 95 97 0  55 20 95 0  93  97                   0.031                                                                              70 95 40 100                                                                              20 0  100                                                                              60 0  10 10 0  0  0  10 0  20  35               305 1.0  97 97 95 100                                                                              80 90 100                                                                              95 90 98 100                                                                              0  93 50 95 0  50  100              306 0.125                                                                              90 100                                                                              70 90 100                                                                              40 -- 100                                                                              0  0  40 0  0  -- 80 0  20  70               __________________________________________________________________________

Certain of the compounds of this invention have been found to be usefulfor the control of aquatic weeds and some of these are useful for theselective control of, e.g., barnyardgrass and yellow nutsedge in paddyfields in the presence of rice. The following example illustrate theutility of the compounds of this invention in aquatic weed control.

EXAMPLE 96

In testing for such utility, the plant species to be tested weretransplanted into 16 oz. containers into about 2 inches of soil whenthey were in the 1-2 inch stage and then flooded to a depth of about 1inch. An acetone concentrate of the chemical to be tested was theninjected into the paddy water, the volume injected being varied asdesired to provide the desired concentration. Percent control wasevaluated nine days after application. The results were as follows:

    ______________________________________                                        CONTROL OF AQUATIC PLANT SPECIES                                                      Dosage    Plant Species                                               Compound  (Kg/Ha)     K     N       S   T                                     ______________________________________                                         1        2.0         97    95      90  70                                     2        2.0         97    97      99  93                                     4        2.0         90    95      45  80                                     6        1.0         93    99      20  90                                     7        1.0         97    99      93  90                                     8        1.0         97    99       0  93                                     9        1.0         25    99      97  85                                              0.25         0    93      80  30                                    10        1.0         93    90      50  90                                    12        1.0         70    97       0  95                                    13        0.25        97    93      10  93                                    15        4.0         35    25       0  70                                    17        4.0         97    40       0  90                                    22        0.25        97    97      30  97                                    25        0.25        97    95       0  90                                    26        0.125       93    90       0  95                                    31        0.125       90    97      45  97                                    32        0.5         93    97      95  95                                    33        1.0         97    97      90  97                                    38        0.25        97    99      85  97                                              0.031        0    80       0  95                                    39        0.25        75    99      75  99                                              0.031        0    20       0  85                                    41        1.0         97    99      95  80                                    49        0.5         97    97      97  99                                              0.016        0    50       0  95                                    50        0.125       97    97      97  97                                    51        1.0         95    97      70  97                                              0.031        0    35       0  93                                    53        0.5         99    99      97  99                                              0.031        0    80      10  95                                    54        0.5         97    97       0  95                                    108       1.0         97    97      97  90                                    111       4.0         93    99      80  99                                    114       1.0         70    95       0  90                                              0.25         0    80       0  65                                    143       0.5         95    99      97  97                                              0.031        0    95       0  93                                    ______________________________________                                    

It has further been found that soil nitrogen may be conserved and plantnutrition improved by treating plant growth media with the novelcompounds of this invention.

By the practice of the embodiment of the invention, the nitrification ofammonium nitrogen in the soil to nitrate nitrogen is suppressed, therebypreventing the rapid loss of ammonium nitrogen from the soil.Furthermore, by proper distribution of the novel compounds, this actionof inhibiting the transformation of ammonium nitrogen to nitratenitrogen is effective over a prolonged period of time including thosesituations where treated fertilizer is stored for some time before use.The ammonium nitrogen may arise from added ammonium nitrogen fertilizersor be formed in the soil by conversion of the organic nitrogenconstituents found in soil or added thereto as components of organicfertilizers.

The provision of an effective but sublethal dosage of the activeingredient in the soil or growth medium is essential for the practice ofthe present invention. In general, good results are obtained when thegrowth medium is impregnated with the active ingredient in the amount offrom 0.01 part to 100 parts or more by weight per million parts byweight of growth medium. (Hereinafter, the abbreviation ppm whenemployed is meant to designate parts by weight of active ingredient permillion parts by weight of soil or growth medium.) The preferred amountsto be employed are dependent upon the particular situation. Thus, indetermining the amount to be employed, consideration is made not only ofthe treatment need, i.e., soil pH, temperature, soil type, etc., butalso of the mode of application to the soil. When the active ingredientis to be applied in a broadcast application, the concentration mayfrequently be less than in row or band application where for asubstantial depth and width within the vicinity of application there maybe a very high concentration of the active ingredient. When applicationis made near the root zone of growing plants or when application is madeimmediately prior to seeding or transplanting, the amounts supplied arefrequently at a lower rate than when application is made at the end ofthe growing season to prepare the soil for the following season. Bydispersing very large dosages in growth media, a prolonged inhibition ofnitrification may be obtained over a period of many months. Theconcentration of the active ingredient is eventually reduced to aminimum by decomposition in the soil.

In one method for carrying out this embodiment of the invention, theactive ingredient is distributed throughout the growth media in abroadcast application such as by spraying, dusting, distributing inirrigation water, etc. In such application, the active ingredient issupplied in amounts sufficient to permeate the growing area of soil withan amount of from 0.05 to 1000 ppm. In field administration, the activeingredient may be distributed in the soil in the amount of at least 0.05pound per acre (0.056 kg/hectare) and through such cross-section of thesoil as to provide for the presence therein of an effectiveconcentration of the agent. It is usually preferred that the activeingredient be distributed to a depth of at least two inches (5.08 cm)below the soil surface and at a dosage of at least 0.1 pound per acre(0.112 kg/hectare).

In another method for carrying out the present invention, the activeingredient is administered to the growth medium in a band or rowapplication. In such application, administration is made with or withoutcarrier in an amount sufficient to supply to soil or growth medium aconcentration of the active ingredient which may be as high as 4000 ppmor more. After administration with or without discing or dragging,subsequent irrigation or rainfall distributes the active ingredientthroughout the growth medium.

In one embodiment of the present invention, the active ingredient isdistributed throughout the growth media prior to seeding ortransplanting the desired crop plant.

In another embodiment, the soil in the root zone of growing plants istreated with the active ingredient in an amount effective to inhibitnitrification. Oftentimes, it is desirable to treat the soil adjacent toplants, and this procedure may be carried out conveniently inside-dressing operations.

In a further embodiment, soil may be treated with the compoundsfollowing harvest or after fallowing to prevent rapid loss of ammoniumnitrogen and to build up the ammonium nitrogen formed by conversion oforganic nitrogen compounds. Such practice conserves the soil nitrogenfor the following growing season. In such application, the upper limitis primarily an economic consideration.

In an additional embodiment, the soil is treated with the activeingredient in conjunction with the application of reduced nitrogenfertilizers. The treatment with the active ingredient may be carried outprior to, subsequent to or simultaneously with the application offertilizers. Such practice prevents the rapid loss of the ammoniumnitrogen added as fertilizer and of the ammonium nitrogen formed fromorganic nitrogen in fertilizers by the action of soil microorganisms.The administration to the soil of the active ingredient in an ammoniumnitrogen or ammonium nitrogen forming fertilizer composition constitutesa preferred embodiment of the present invention.

The present invention may be carried out by distributing the activeingredient in an unmodified form through growth medium. The presentmethod also embraces distributing the active ingredient as a constituentin liquid or finely divided solid compositions. In such practice, theactive ingredient may be modified with one or more additaments or soiltreating adjuvants including water, petroleum distillates or otherliquid carriers, surface-active dispersing agents, finely divided inertsolids and nitrogen fertilizers. Depending upon the concentration of theactive ingredient, such augmented composition may be distributed in thesoil without further modification or be considered a concentrate andsubsequently diluted with additional inert carrier to produce theultimate treating composition. The required amount of the activeingredient may be supplied to growth media in an organic solventcarrier, in an aqueous carrier or in a solid carrier. When an organicsolvent carrier is employed, it may be further dispersed in an aqueousliquid carrier.

The concentration of the active ingredient in compositions to beemployed for the treatment of growth mediais not critical and may varyconsiderably provided the required dosage of effective agent is suppliedto the growth media. The concentration of the active ingredient may varyfrom 0.00001 percent by weight to 95 percent by weight of thecomposition, depending on whether the composition is a treatingcomposition or a concentrate composition and whether it is in the formof a solid or a liquid. In aqueous liquid treating compositions,concentrations of from 0.00001 percent to 0.25 percent by weight of theactive ingredient is considered the preferred composition. Theconcentration of the active ingredient in organic solvents may be from 2to 95 percent by weight. Concentrate liquid compositions generallycontain from 2.5 to 95 percent by weight of the active ingredient.Treating compositions generally contain from 0.0001 percent to 10percent by weight of the active ingredient while concentratecompositions contain from 2.5 to 95 percent.

Liquid compositions containing the desired amount of the activeingredient may be prepared by dispersing the latter in one or moreliquid carriers such as water or an organic solvent, with or without theaid of a suitable surface-active dispersing agent or emulsifying agent.Suitable organic solvents include acetone, diisobutylketone, methanol,ethanol, isopropyl alcohol, toluene, methylene chloride, chlorobenzeneand the petroleum distillates. The preferred organic solvents are thosewhich are of such volatility that they leave little permanent residue inthe soil. When the solutions of the active ingredient in organicsolvents are to be further diluted to produce aqueous dispersions, thepreferred solvents include acetone and the alcohols. When the liquidcarrier is entirely organic in nature, particularly desirable carriersare the petroleum distillates boiling almost entirely under 400° F.(204° C.) at atmospheric pressure and having a flash point above 100° F.(38° C.). Dispersing and emulsifying agents which may be employed inliquid compositions include condensation products of alkylene oxideswith phenols and organic acids, alkyl aryl sulfonates, polyoxyalkylenederivatives of sorbitan esters, complex ether alcohols, mahogany soapsand the like. The surface-active agents are generally employed in theamount of from 1 to 20 percent by weight of the active ingredient.

Solid compositions containing the active ingredient may be prepared bydispersing the latter in finely divided inert solid carriers such astalc, chalk, gypsum, vermiculite, bentonite and the like, fuller'searth, attapulgite and other clays, various solid detergent dispersingagents and solid fertilizer compositions. In preparing suchcompositions, the carrier is mechanically ground with the activeingredient or wet with a solution or dispersion thereof in a volatileorganic solvent. Depending upon the proportions of ingredients, thesecompositions may be employed without further modification or beconsidered concentrates and subsequently further diluted with solidsurface-active dispersing agent, talc, chalk, gypsum or the like toobtain the desired treating composition. Furthermore, such concentratecompositions have the properties of wettable powders and may bedispersed in water with or without added dispersing agent or agents toprepare aqueous soil treating compositions.

Soil treatment compositions may be prepared by dispersing the activeingredient in fertilizers such as ammonium fertilizer or organicnitrogen fertilizer. The resulting fertilizer composition may beemployed as such or may be modified as by dilution with additionalnitrogen fertilizer or with inert solid carrier to obtain a compositioncontaining the desired amount of active agent for the treatment of soil.Further, an aqueous dispersion of the active ingredient-fertilizercomposition may be prepared and administered to the growth medium.Fertilizer compositions comprising the active ingredient in intimateadmixture with ammonium fertilizers constitute preferred embodiments ofthe present invention.

In fertilizer compositions comprising a reduced nitrogen fertilizer, itis desirable that the active ingredient be present in an amount of atleast 0.05 percent by weight based on the weight of the nitrogen presentin the fertilizer as reduced nitrogen and may be present in amounts ashigh as 95 percent by weight of the reduced nitrogen in the fertilizer.Thus, when a fertilizer composition contains both reduced nitrogen andother forms of nitrogen such as in the case of ammonium nitratefertilizer compositions, the amount of the active ingredient is based onthe weight of nitrogen present in the ammonium component.

In operations carried out in accordance with the present invention, thesoil may be treated in any convenient fashion with the active compoundor a composition containing the latter. For example, these modified orunmodified compositions may be mechanically mixed with soil; applied tothe surface of soil and thereafter dragged or disced into the soil to adesired depth; or transported into the soil with a liquid carrier wuchas by injection, spraying or irrigation. When the distribution iscarried out by introducing the compound in the water employed toirrigate the soil, the amount of water is varied in accordance with themoisture content of the soil in order to obtain a distribution of thecompound to the desired depth. The compound may be readily andconveniently distributed to a depth of a few inches to four feet byirrigation methods. The preferred methods embrace procedures using anyof these steps or combination of steps wherein the compound isdistributed in the soil substantially simultaneously with a reducednitrogen fertilizer.

A number of the compounds of this invention were tested for theirability to reduce the rate of nitrification of ammonium nitrogen,applied as ammonium phosphate to the soil. The activity is reported inthe following table.

EXAMPLE 97

The test method comprised selecting a soil which had a low nitrateconcentration and good nitrification activity. A sufficient volume ofwater was added to 20 g of the soil in a wide-mouth, screw-cap, 4-ounce,glass bottle, such that the moisture content of the mixture was madeequal to the 1/3 bar tension value for that soil. The mixture wasthoroughly mixed before sealing. The added water contained 5 mg (250ppm) of nitrogen in the form of (NH₄)₂ HPO₄ (23.6 mg of ammoniumphosphate) and the desired quantity of test chemical (i.e., 20 mg for a1 ppm concentration based on dry weight of soil). When the test chemicalhad a low water solubility, it was compounded in acetone (or othersuitable solvent) in such a way that the final mixture in the soilcontained no more than 10 μl of acetone. Acetone slows the rate of soilnitrification and its concentration must be carefully controlled. Singlesamples of each test chemical were incubated for two weeks at 27° C.

The experiment comprised the following types of samples:

1. Nitrate blank containing soil, water and solvent only. (BLANK)

2. Test chemicals containing soil, water, ammonium phosphate, solvent,and test chemical. Single samples. (SAMPLE)

3. Nitrate control containing soil, water and ammonium phosphate only.(CONTROL)

The soil samples were analyzed as follows: Sufficient ammonium sulfateextracting solution was added to the sample, such that the total volumeof added water was 50 ml (included water added during samplepreparation). The capped mixture was shaken 10 minutes to solubilizenitrate and the soil particulates were allowed to settle. The nitrateconcentration in the water phase was determined with a nitrate-specificion electrode such as Orion Model 93-07.

The non-nitrate nitrogen remaining (% NH₄ --N remaining) in the soilafter two weeks (performance value) was calculated as follows: ##EQU1##

    __________________________________________________________________________    % NH.sub.4 --N Remaining                                                      After 2 Weeks Incubation                                                      at Indicated Concentration (ppm)                                              Compound                                                                            10 5 4 2.5                                                                             1.25                                                                             1 0.6                                                                             0.5                                                                             0.25                                                                             0.125                                                                            0.1                                                                             0.06                                                                             0.01                                       __________________________________________________________________________    1     75 --                                                                              --                                                                              --                                                                              -- 35                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          2     78 --                                                                              --                                                                              --                                                                              -- 39                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          3     25 --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 0 -- 0                                          4     71 --                                                                              --                                                                              --                                                                              -- 38                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          5     28 --                                                                              --                                                                              --                                                                              -- 1 --                                                                              --                                                                              -- -- 0 -- 0                                          6     87 --                                                                              --                                                                              --                                                                              -- 78                                                                              --                                                                              --                                                                              -- -- 55                                                                              -- 15                                         7     -- --                                                                              --                                                                              --                                                                              -- 80                                                                              --                                                                              73                                                                              62 30 --                                                                              17 --                                         8     -- --                                                                              --                                                                              --                                                                              -- 67                                                                              --                                                                              59                                                                              44 23 --                                                                              4  --                                         9     88 --                                                                              --                                                                              --                                                                              -- 59                                                                              --                                                                              --                                                                              -- -- 14                                                                              -- 0                                          10    70 --                                                                              --                                                                              --                                                                              -- 27                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          11    5  --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 0 -- 0                                          12    -- --                                                                              --                                                                              --                                                                              -- 87                                                                              --                                                                              83                                                                              74 70 --                                                                              40 --                                         13    -- --                                                                              --                                                                              --                                                                              -- 89                                                                              --                                                                              85                                                                              81 78 --                                                                              73 --                                         14    77 --                                                                              --                                                                              --                                                                              -- 52                                                                              --                                                                              --                                                                              -- -- 10                                                                              -- 0                                          15    -- --                                                                              --                                                                              --                                                                              -- 54                                                                              --                                                                              42                                                                              23 0  --                                                                              1  --                                         16    67 --                                                                              --                                                                              --                                                                              -- 26                                                                              --                                                                              --                                                                              -- 0  --                                                                              -- 0                                          17    80 --                                                                              --                                                                              --                                                                              -- 38                                                                              --                                                                              --                                                                              -- -- 1 -- 0                                          18    50 --                                                                              --                                                                              --                                                                              -- 5 --                                                                              --                                                                              -- -- 0 -- 0                                          20    -- --                                                                              --                                                                              --                                                                              -- 8 --                                                                              5 0  0  --                                                                              0  --                                         21    86 --                                                                              --                                                                              --                                                                              -- 68                                                                              --                                                                              --                                                                              -- -- 42                                                                              -- 8                                          22    -- --                                                                              --                                                                              --                                                                              -- 86                                                                              --                                                                              86                                                                              82 77 --                                                                              69 --                                         24    83 --                                                                              --                                                                              --                                                                              -- 65                                                                              --                                                                              --                                                                              -- -- 28                                                                              -- 0                                          25    -- --                                                                              --                                                                              --                                                                              -- 79                                                                              --                                                                              73                                                                              48 46 --                                                                              31 --                                         26    -- --                                                                              --                                                                              --                                                                              -- 79                                                                              --                                                                              73                                                                              65 45 --                                                                              37 --                                         27    35 --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 0 -- 0                                          28    66 --                                                                              --                                                                              --                                                                              -- 42                                                                              --                                                                              --                                                                              -- -- 5 -- 0                                          29    51 --                                                                              --                                                                              --                                                                              -- 1 --                                                                              --                                                                              -- -- 0 -- 0                                          30    81 --                                                                              --                                                                              --                                                                              -- 54                                                                              --                                                                              --                                                                              -- -- 6 -- 0                                          31    91 --                                                                              --                                                                              --                                                                              -- 86                                                                              --                                                                              --                                                                              -- -- 66                                                                              -- 0                                          32    100                                                                              --                                                                              --                                                                              --                                                                              -- 82                                                                              --                                                                              --                                                                              -- -- 33                                                                              -- 0                                          33    88 --                                                                              --                                                                              --                                                                              -- 77                                                                              --                                                                              --                                                                              -- -- 42                                                                              -- 8                                          34    90 --                                                                              --                                                                              --                                                                              -- 78                                                                              --                                                                              --                                                                              -- -- 51                                                                              -- 11                                         35    78 --                                                                              --                                                                              --                                                                              -- 50                                                                              --                                                                              --                                                                              -- -- 3 -- 0                                          36    60 --                                                                              --                                                                              --                                                                              -- 17                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          37    44 --                                                                              --                                                                              --                                                                              -- 7 --                                                                              --                                                                              -- -- 0 -- 0                                          38    94 --                                                                              --                                                                              --                                                                              -- 84                                                                              --                                                                              --                                                                              -- -- 68                                                                              -- 46                                         39    100                                                                              --                                                                              --                                                                              --                                                                              -- 91                                                                              --                                                                              --                                                                              -- -- 78                                                                              -- 49                                         40    66 17                                                                              --                                                                              40                                                                              0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         41    100                                                                              --                                                                              --                                                                              --                                                                              -- 87                                                                              --                                                                              --                                                                              -- -- 54                                                                              -- 23                                         42    68 --                                                                              --                                                                              --                                                                              -- 8 --                                                                              --                                                                              -- -- 0 -- 0                                          43    91 --                                                                              --                                                                              --                                                                              -- 44                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          44    95 --                                                                              --                                                                              --                                                                              -- 71                                                                              --                                                                              --                                                                              -- -- 42                                                                              -- 0                                          45    94 --                                                                              --                                                                              --                                                                              -- 45                                                                              --                                                                              --                                                                              -- -- 3 -- 0                                          46    94 --                                                                              --                                                                              --                                                                              -- 88                                                                              --                                                                              --                                                                              -- -- 71                                                                              -- 50                                         47    92 --                                                                              --                                                                              --                                                                              -- 73                                                                              --                                                                              --                                                                              -- -- 40                                                                              -- 0                                          48    93 --                                                                              --                                                                              --                                                                              -- 56                                                                              --                                                                              --                                                                              -- -- 3 -- 0                                          49    99 --                                                                              --                                                                              --                                                                              -- 90                                                                              --                                                                              --                                                                              -- -- 77                                                                              -- 42                                         50    92 --                                                                              --                                                                              --                                                                              -- 73                                                                              --                                                                              --                                                                              -- -- 38                                                                              -- 40                                         51    -- --                                                                              87                                                                              --                                                                              -- 78                                                                              --                                                                              --                                                                              58 -- --                                                                              33 --                                         52    91 --                                                                              --                                                                              --                                                                              -- 74                                                                              --                                                                              --                                                                              -- -- 39                                                                              -- 0                                          53    93 --                                                                              --                                                                              --                                                                              -- 85                                                                              --                                                                              --                                                                              -- -- 71                                                                              -- 47                                         54    -- --                                                                              76                                                                              --                                                                              -- 66                                                                              --                                                                              --                                                                              51 -- --                                                                              20 --                                         55    -- --                                                                              84                                                                              --                                                                              -- 65                                                                              --                                                                              --                                                                              91 -- --                                                                              19 --                                         56    -- --                                                                              78                                                                              --                                                                              -- 59                                                                              --                                                                              --                                                                              37 -- --                                                                              0  --                                         57    -- --                                                                              69                                                                              --                                                                              -- 45                                                                              --                                                                              --                                                                              17 -- --                                                                              2  --                                         58    -- --                                                                              80                                                                              --                                                                              -- 58                                                                              --                                                                              --                                                                              48 -- --                                                                              92 --                                         59    -- --                                                                              66                                                                              --                                                                              -- 51                                                                              --                                                                              --                                                                              33 -- --                                                                              11 --                                         60    58 41                                                                              --                                                                              8 0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         61    100                                                                              89                                                                              --                                                                              65                                                                              34 --                                                                              20                                                                              --                                                                              -- -- --                                                                              -- --                                         62    75 55                                                                              --                                                                              --                                                                              13 --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         63    -- --                                                                              61                                                                              --                                                                              -- 36                                                                              --                                                                              --                                                                              6  -- --                                                                              6  --                                         64    -- --                                                                              81                                                                              --                                                                              -- 62                                                                              --                                                                              --                                                                              43 -- --                                                                              19 --                                         65    -- --                                                                              85                                                                              --                                                                              -- 65                                                                              --                                                                              --                                                                              52 -- --                                                                              5  --                                         66    -- --                                                                              78                                                                              --                                                                              -- 66                                                                              --                                                                              --                                                                              41 -- --                                                                              0  --                                         67    -- --                                                                              69                                                                              --                                                                              -- 41                                                                              --                                                                              --                                                                              0  -- --                                                                              0  --                                         68    -- --                                                                              57                                                                              --                                                                              -- 16                                                                              --                                                                              --                                                                              20 -- --                                                                              0  --                                         70    -- --                                                                              87                                                                              --                                                                              -- 69                                                                              --                                                                              --                                                                              29 -- --                                                                              0  --                                         71    -- --                                                                              90                                                                              --                                                                              -- 84                                                                              --                                                                              --                                                                              49 -- --                                                                              35 --                                         73    -- --                                                                              62                                                                              --                                                                              -- 41                                                                              --                                                                              --                                                                              47 -- --                                                                              26 --                                         75    -- --                                                                              86                                                                              --                                                                              -- 67                                                                              --                                                                              --                                                                              61 -- --                                                                              25 --                                         76    -- --                                                                              86                                                                              --                                                                              -- 74                                                                              --                                                                              --                                                                              52 -- --                                                                              34 --                                         77    -- --                                                                              71                                                                              --                                                                              -- 34                                                                              --                                                                              --                                                                              80 -- --                                                                              17 --                                         78    -- --                                                                              72                                                                              --                                                                              -- 53                                                                              --                                                                              --                                                                              32 -- --                                                                              74 --                                         80    -- --                                                                              43                                                                              --                                                                              -- 20                                                                              --                                                                              --                                                                              0  -- --                                                                              0  --                                         91    -- --                                                                              80                                                                              --                                                                              -- 55                                                                              --                                                                              --                                                                              46 -- --                                                                              15 --                                         92    -- --                                                                              25                                                                              --                                                                              -- 0 --                                                                              --                                                                              4  -- --                                                                              0  --                                         93    -- --                                                                              89                                                                              --                                                                              -- 64                                                                              --                                                                              --                                                                              57 -- --                                                                              79 --                                         94    -- --                                                                              84                                                                              --                                                                              -- 56                                                                              --                                                                              --                                                                              48 -- --                                                                              28 --                                         95    -- --                                                                              67                                                                              --                                                                              -- 53                                                                              --                                                                              --                                                                              36 -- --                                                                              26 --                                         96    100                                                                              42                                                                              --                                                                              7 0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         97    -- --                                                                              19                                                                              --                                                                              -- 3 --                                                                              --                                                                              0  -- --                                                                              67 --                                         98    -- --                                                                              37                                                                              --                                                                              -- 0 --                                                                              --                                                                              25 -- --                                                                              0  --                                         99    -- --                                                                              57                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         102   44 24                                                                              --                                                                              0 0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         103   -- --                                                                              53                                                                              --                                                                              -- 43                                                                              --                                                                              --                                                                              15 -- --                                                                              0  --                                         106   96 --                                                                              --                                                                              --                                                                              -- 88                                                                              --                                                                              --                                                                              -- -- 56                                                                              -- 29                                         108   90 --                                                                              --                                                                              --                                                                              -- 84                                                                              --                                                                              --                                                                              -- -- 69                                                                              -- 43                                         109   92 --                                                                              --                                                                              --                                                                              -- 41                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          110   59 --                                                                              --                                                                              --                                                                              -- 13                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          111   -- --                                                                              92                                                                              --                                                                              -- 69                                                                              --                                                                              --                                                                              60 -- --                                                                              22 --                                         112   -- --                                                                              72                                                                              --                                                                              -- 65                                                                              --                                                                              --                                                                              53 -- --                                                                              31 --                                         113   -- --                                                                              86                                                                              --                                                                              -- 69                                                                              --                                                                              --                                                                              39 -- --                                                                              16 --                                         115   -- --                                                                              86                                                                              --                                                                              -- 64                                                                              --                                                                              --                                                                              41 -- --                                                                              37 --                                         116   -- --                                                                              81                                                                              --                                                                              -- 57                                                                              --                                                                              --                                                                              50 -- --                                                                              27 --                                         117   -- --                                                                              72                                                                              --                                                                              -- 41                                                                              --                                                                              --                                                                              24 -- --                                                                              32 --                                         118   -- --                                                                              85                                                                              --                                                                              -- 61                                                                              --                                                                              --                                                                              37 -- --                                                                              30 --                                         119   -- --                                                                              88                                                                              --                                                                              -- 69                                                                              --                                                                              --                                                                              33 -- --                                                                              23 --                                         120   -- --                                                                              87                                                                              --                                                                              -- 63                                                                              --                                                                              --                                                                              46 -- --                                                                              71 --                                         135   100                                                                              --                                                                              --                                                                              --                                                                              -- 12                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          136   98 --                                                                              --                                                                              --                                                                              -- 67                                                                              --                                                                              --                                                                              -- -- 10                                                                              -- 0                                          142   98 --                                                                              --                                                                              --                                                                              -- 62                                                                              --                                                                              --                                                                              -- -- 5 -- 0                                          143   100                                                                              --                                                                              --                                                                              --                                                                              -- 91                                                                              --                                                                              --                                                                              -- -- 78                                                                              -- 50                                         144   -- --                                                                              92                                                                              --                                                                              -- 63                                                                              --                                                                              --                                                                              43 -- --                                                                              16 --                                         146   -- --                                                                              79                                                                              --                                                                              -- 60                                                                              --                                                                              --                                                                              48 -- --                                                                              19 --                                         147   -- --                                                                              87                                                                              --                                                                              -- 72                                                                              --                                                                              --                                                                              55 -- --                                                                              41 --                                         148   93 89                                                                              --                                                                              81                                                                              75 --                                                                              69                                                                              --                                                                              -- -- --                                                                              -- --                                         149   62 26                                                                              --                                                                              5 0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         150   -- --                                                                              93                                                                              --                                                                              -- 91                                                                              --                                                                              --                                                                              74 -- --                                                                              83 --                                         159   -- --                                                                              94                                                                              --                                                                              -- 80                                                                              --                                                                              --                                                                              56 -- --                                                                              49 --                                         178   91 --                                                                              --                                                                              --                                                                              -- 43                                                                              --                                                                              --                                                                              -- -- 0 -- --                                         192   -- --                                                                              86                                                                              --                                                                              -- 74                                                                              --                                                                              --                                                                              48 -- --                                                                              21 --                                         198   -- --                                                                              74                                                                              --                                                                              -- 53                                                                              --                                                                              --                                                                              37 -- --                                                                              22 --                                         199   -- --                                                                              88                                                                              --                                                                              -- 78                                                                              --                                                                              --                                                                              63 -- --                                                                              40 --                                         200   -- --                                                                              60                                                                              --                                                                              -- 50                                                                              --                                                                              --                                                                              31 -- --                                                                              0  --                                         201   -- --                                                                              67                                                                              --                                                                              -- 56                                                                              --                                                                              --                                                                              11 -- --                                                                              0  --                                         202   -- --                                                                              32                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         204   66 56                                                                              --                                                                              34                                                                              0  --                                                                              0 --                                                                              -- -- --                                                                              -- --                                         205   -- --                                                                              81                                                                              --                                                                              -- 76                                                                              --                                                                              --                                                                              38 -- --                                                                              32 --                                         208   -- --                                                                              37                                                                              --                                                                              -- 42                                                                              --                                                                              --                                                                              38 -- --                                                                              38 --                                         224   -- --                                                                              63                                                                              --                                                                              -- 27                                                                              --                                                                              --                                                                              0  -- --                                                                              1  --                                         226   -- --                                                                              69                                                                              --                                                                              -- 42                                                                              --                                                                              --                                                                              17 -- --                                                                              2  --                                         245   -- --                                                                              30                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         247   -- --                                                                              82                                                                              --                                                                              -- 58                                                                              --                                                                              --                                                                              47 -- --                                                                              58 --                                         251   29 --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 0 -- 0                                          252   82 --                                                                              --                                                                              --                                                                              -- 38                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          253   17 --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 5 -- 0                                          255   72 --                                                                              --                                                                              --                                                                              -- 37                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          256   48 --                                                                              --                                                                              --                                                                              -- 10                                                                              --                                                                              --                                                                              -- -- 13                                                                              -- 20                                         257   58 --                                                                              --                                                                              --                                                                              -- 0 --                                                                              --                                                                              -- -- 0 -- 0                                          258   78 --                                                                              --                                                                              --                                                                              -- 23                                                                              --                                                                              --                                                                              -- -- 0 -- 0                                          259   -- --                                                                              40                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         260   -- --                                                                              45                                                                              --                                                                              -- 37                                                                              --                                                                              --                                                                              14 -- --                                                                              0  --                                         261   -- --                                                                              18                                                                              --                                                                              -- 21                                                                              --                                                                              --                                                                              0  -- --                                                                              0  --                                         262   -- --                                                                              89                                                                              --                                                                              -- 75                                                                              --                                                                              --                                                                              49 -- --                                                                              28 --                                         263   -- --                                                                              11                                                                              --                                                                              -- 87                                                                              --                                                                              --                                                                              0  -- --                                                                              0  --                                         264   -- --                                                                              37                                                                              --                                                                              -- 26                                                                              --                                                                              --                                                                              1  -- --                                                                              0  --                                         265   -- --                                                                              17                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         266   -- --                                                                              13                                                                              --                                                                              -- 2 --                                                                              --                                                                              0  -- --                                                                              0  --                                         267   -- --                                                                              11                                                                              --                                                                              -- 0 --                                                                              --                                                                              0  -- --                                                                              0  --                                         268   -- --                                                                              92                                                                              --                                                                              -- 80                                                                              --                                                                              --                                                                              71 -- --                                                                              53 --                                         __________________________________________________________________________

Additionally, certain compounds of the present invention may be used tomodify plant growth benefically such as the inhibition of bolting insugarbeets. Other compounds of the present invention alter the normalgrowth of sugarbeets by stunting the plant. Both of the effectsdescribed above are not accompanied by any phytotoxic symptoms.

Sugar beet flowering is controlled by a cold weather treatment of theplants (vernalization) followed by long days. As the days lengthen, thebeets produce bolters--elongated stems bearing flowers--and ultimatelyseeds on indeterminate, multibranced racemes. In Europe where a largeacreage of sugar beet is grown, cold spring weather following sowing isoften enough to induce bolting of the beets. This bolting causes variousproblems to the farmer who grows the beet for the sugar content of thebeet root. The problems are numerous:

1. Bolting reduces both the size and the sugar content of the beet rootsince the products of photosynthesis are diverted to flower production.

2. Bolting causes processing difficulties due to lignification of theroot. Lignification uses up stored sugars as well, thus reducing theefficiency of the extraction process.

3. Bolters physically interfere with mechanical harvesting by becomingentangled in harvesting machinery.

4. Bolted plants cause a large amount of competition by shading ofadjacent plants, thereby reducing their root size.

5. With time, the seed from early bolters have produced a weed beet withan annual habit requiring little or no vernalization. This weed beet,besides causing severe competition, prevents "beet-free periods" whichare necessary for the control of beet yellowing virus.

If bolting could be completely prevented, this would be a possible meansof realizing the potential physiological advantages of autumn sowing.Greater utilization of the season would be achieved by the capturing orradiation which normally falls on bare ground. Yield increases of up to25% have been predicted from autumn as opposed to spring sowing. Even anearlier spring sowing promises an increase in yield. The followingexample illustrates the plant growth regulator effects of the compoundsof this invention.

EXAMPLE 98

Using a regular biennial variety, even a bolting-susceptible varietywould require a cold treatment of around 10-16 weeks plus a hormonetreatement in conjunction with specific light intensities. Thus, for ascreening organism, we selected one which would consistently producebolting on a regular schedule. The screen is run with an annual sugarbeet variety (SLC03) provided by Dr. Richard J. Hecker, Fort Collins,Colo. This variety is an inbred which bolts in the 6- to 8-leaf stagewithout any need for vernalization. This allows the screen to be runentirely in the greenhouse with all 110 chemical compounds tested on onetray. The sugarbeets are grown in 3×3 inch square pots in a greenhousesandy loam potting mix. The sugarbeets are sprayed with test compoundswhen they are 2 to 3 weeks old (2 true leaves). The compounds aredissolved in acetone and diluted with water containing Tween 20 as awetting agent. The concentration of acetone in the final spray is 20%and the concentration of Tween 20 is 0.05 percent. The plants areexamined for the appearance of a bolt 4 weeks after spraying.

Preemergence tests are conducted by spraying formulated chemical onseeds placed on potting soil. The sprayed seeds are then covered with1/4 inch of potting soil and the pots are watered. Bolting is evaluated6-7 weeks after the initiation of the test. At this time untreatedplants have a vigorous bolting stem with visible flowers.

    ______________________________________                                        Plant Growth Regulator Activity                                               Observed Effect at Concentration Indicated                                             Bolting         Bolting                                                       Inhibition      Inhibition                                           Compound (postemergence) (preemergence)                                       ______________________________________                                        8        50     ppm                                                           14                           400  ppm                                         16                           400  ppm                                         52                           100  ppm                                         63       5      ppm                                                           65       12     ppm                                                           66                           400  ppm                                         71                           400  ppm                                         77       12     ppm                                                           95                           400  ppm                                         98       400    ppm                                                           119      400    ppm (stunting)                                                129      400    ppm          400  ppm                                         132                          400  ppm                                         133                          400  ppm (stunting)                              134                          400  ppm (stunting)                              198                          400  ppm (stunting)                              204      400    ppm                                                                    200    ppm                                                           267      400    ppm (stunting)                                                ______________________________________                                    

EXAMPLE 99

The compounds of this invention are also plant gametocides depending onthe dosage and timing of application and the species of plant to whichthe compounds are applied. For example, certain of the compounds weresprayed on corn seedlings at the three leaf stage of growth, and theseedlings were returned to the greenhouse for subsequent growth andobservation. The corn variety was "First In". The chemicals weredissolved in acetone, and the acetone solution was diluted with watercontaining Tween 20 wetting agent such that the final spray solutioncontained 50% acetone and 0.1% Tween 20 in water. At the time of tasselformation the anthers appeared normal, but they did not contain pollen.Tabulated below are data which illustrate the use of the compounds ofthis invention as plant gametocides in corn.

    ______________________________________                                        Gametocidal Activity in Corn                                                  (Postemergent Application)                                                    Compound     Concentration (ppm)*                                             ______________________________________                                        275          400                                                              277          200                                                              279           50                                                              ______________________________________                                         *concentration required to produce 100% control.                         

We claim:
 1. Method for inhibiting pollen formation in corn whichcomprises the application of a pollen inhibiting amount of a compoundhaving the formula: ##STR94## wherein Ar represents an aromatic orheteroaromatic ring chosen from among phenyl; 1- or 2-naphthyl; 2-, 3-or 4-pyridyl; 2- or 3-thienyl; 2- or 3-furyl; 2-, 4- or 5-thiazoyl; 2-,4- or 5-imidazoyl; 2-, 4- or 5-oxazoyl; 3-, 4- or 5-isothiazoyl; 3-, 4-or 5-isoxazoyl; 3-, 4- or 5-pyrazoyl; 2-benzthiazoyl; 2-benzoxazoyl;2-benzimidazoyl or 1-benztriazoyl; and Ar is unsubstituted or Ar issubstituted with one to five substituents chosen from among (except inthe cases of thio, sulfinyl and sulfonyl substituents where if one ofthese substituents is present the other one to four Ar substituents maynot be chosen from among the other two); oxycarbonyl substituents wherethe other one to four Ar substituents may not be chosen from amongdifferent oxycarbonyl; or aminocarbonyl substituents; where the otherone to four Ar substituents may not be chosen from among differentaminocarbonyl substituents; C₁ -C₆ alkyl; halo; C₁ -C₆ mono- orpolyhaloalkyl; phenyl; hydroxy; C₁ -C₆ alkoxy; C₁ -C₆ mono- orpolyhaloalkoxy; phenoxy; phenoxy substituted with one or more of groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; 2-pyridyloxy;2-pyridyloxy substituted with one or more of groups chosen from halo, C₁-C₆ alkyl or C₁ -C₆ haloalkyl; C₁ -C₆ alkylamino; C₁ -C₆ dialkylamino;nitro; C₁ -C₆ alkylthio; C₁ -C₆ polyhaloalkylthio; C₁ -C₆ alkylsulfinyl;C₁ -C₆ polyhaloalkylsulfinyl; C₁ -C₆ alkylsulfonyl; C₁ -C₆polyhaloalkylsulfonyl; phenylthio; phenylthio substituted with one ormore of groups chosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;phenylsulfinyl; phenylsulfinyl substituted with one or more of groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; phenylsulfonyl;phenylsulfonyl substituted with one or more of groups chosen from halo,C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; cyano; carboxyl; C₁ -C₁₀alkoxycarbonyl; phenoxycarbonyl; phenoxycarbonyl substituted with one ormore of groups chosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;alkoxyalkoxycarbonyl wherein the number of carbons in the alkoxyalkoxyfragment ranges from 2-10 and the number of oxygens in the alkoxyalkoxyfragment ranges from 2-4; 2-pyridylmethoxycarbonyl;dialkylaminoalkoxycarbonyl wherein the number of carbons in the dialkylaminoalkoxy fragment ranges from 3- 10 and the number of oxygens in thedialkylaminoalkoxy fragment is one; C₁ -C₆ alkenyloxycarbonyl;COON═C(R¹)(R²) wherein R¹ and R² independently represent hydrogen, C₁-C₆ alkyl or phenyl; unsubstituted, N--C₁ -C₆ alkyl or N,N-di-C₁ -C₆alkylaminocarbonyl; C₁ -C₁₀ dialkylaminosulfonyl; formyl; C₁ -C₆alkylcarbonyl; C₁ -C₆ mono- or polyhaloalkylcarbonyl; phenylcarbonyl;phenylcarbonyl substituted with one or more of groups chosen from halo,C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; or C(R³)(R⁴)OR⁵ wherein R³ and R⁴independently represent hydrogen or C₁ -C₆ alkyl and R⁵ representshydrogen, C₁ -C₆ alkyl, benzyl, phenylcarbonyl or C₁ -C₆ alkylcarbonyl;X, Y and Z independently represent hydroxyl, carboxyl, hydrogen, C₁ -C₆alkyl, C₁ -C₆ mono- or polyhaloalkyl, C₁ -C₆ alkoxy, C₁ -C₆ mono- orpolyhaloalkoxy, phenyl, phenyl substituted with one or more groupschosen from halo, nitro, C₁ -C₆ alkyl or C₁ -C₆ mono- or polyhaloalkyl,C₁ -C₆ alkylthio, halogen, or two adjacent substituents (i.e. X and Y orY and Z) are joined together to form a saturated five, six orseven-membered saturated cyclic structure of carbon atoms or one carbonatom of X,Y or Y,Z is replaced by a heteroatom chosen from amongnitrogen, oxygen or sulfur (i.e. X,Y or Y,Z is --(CH₂)_(n) -- wherein nis 3, 4 or 5; or X,Y or Y,Z is --(CH₂)_(n) --A--(CH₂)_(m) wherein n is0-4, the value of m is equal to the ring size minus (n+3) and A is NH, Oor S) and R represents alkyl, alkenyl, alkynyl, phenylalkyl, acyl,alkoxycarbonyl, phenoxycarbonyl, dialkylaminocarbonyl, alkylsulfonyl,phenylsulfonyl, alkylthiocarbonyl or phenylthiocarbonyl wherein alkyl,alkenyl, alkynyl and alkoxy in each instance have from 1 to 10 carbonatoms.
 2. Method of claim 1 which comprises the application of a polleninhibiting amount of a compound wherein Ar represents substituted orunsubstituted phenyl; 1- or 2-naphthyl; 2-, 3- or 4-pyridyl; 2- or3-thienyl; or 3-, 4- or 5-pyrazolyl.
 3. Method of claim 1 whichcomprises the application of a pollen inhibiting amount of a compoundwherein Ar represents substituted phenyl, substituted 1-naphthyl orsubstituted 4-pyrazolyl.
 4. Method of claim 1 which comprises theapplication of a pollen inhibiting amount of a compound wherein Ar is##STR95## wherein R¹, R², R³, R⁴ and R⁵ independently represent (exceptin the case of thio, sulfinyl or sulfonyl substituents where if one ofthese substituents is present the other one to four Ar substituents maynot be chosen from among the other two; oxycarbonyl substituents wherethe other one to four Ar substituents may not be chosen from amongdifferent oxycarbonyl substituents; or aminocarbonyl substituents wherethe other one to four Ar substituents may not be chosen from amongdifferent aminocarbonyl substituents) H; C₁ -C₆ alkyl; halo; C₁ -C₆mono- or polyhaloalkyl; phenyl; hydroxy; C₁ -C₆ alkoxy; C₁ -C₆ mono- orpolyhaloalkoxy; phenoxy; phenoxy substituted with one or more of groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; 2-pyridyloxy;2-pyridyloxy substituted with one or more of groups chosen from halo, C₁-C₆ alkyl or C₁ -C₆ haloalkyl; C₁ -C₆ alkylamino; C₁ -C₆ dialkylamino;nitro; C₁ -C₆ alkylthio; C₁ -C₆ polyhaloalkylthio; C₁ -C₆ alkylsulfinyl;C₁ -C₆ polyhaloalkylsulfinyl; C₁ -C₆ alkylsulfonyl; C₁ -C₆polyhaloalkylsulfonyl; phenylthio; phenylthio substituted with one ormore of groups chosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;phenylsulfinyl; phenylsulfinyl substituted with one or more of groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; phenylsulfonyl;phenylsulfonyl substituted with one or more of groups chosen from halo,C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; cyano; carboxyl; C₁ -C₁₀alkoxycarbonyl; phenoxycarbonyl; phenoxycarbonyl substituted with one ormore of groups chosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;alkoxyalkoxycarbonyl wherein the number of carbons in the alkoxyalkoxyfragment ranges from 2-10 and the number of oxygens in the alkoxyalkoxyfragment ranges from 2-4; 2-pyridylmethoxycarbonyl;dialkylaminoalkoxycarbonyl wherein the number of carbons in thedialkylaminoalkoxy fragment ranges from 3-10 and the number of oxygensin the dialkylaminoalkoxy fragment is one; C₁ -C₆ alkenyloxycarbonyl;COON═C(R⁶)(R⁷) wherein R⁶ and R⁷ independently represent hydrogen, C₁-C₆ alkyl or phenyl; unsubstituted, N--C₁ -C₆ alkyl or N,N-di-C₁ -C₆alkylaminocarbonyl; C₁ -C₁₀ dialkylaminosulfonyl; formyl; C₁ -C₆alkylcarbonyl; C₁ -C₆ mono- or polyhaloalkylcarbonyl; phenylcarbonyl;phenylcarbonyl substituted with one or more of groups chosen from halo,C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; or C(R⁸)(R⁹)OR¹⁰ wherein R⁸ and R⁹independently represent hydrogen or C₁ -C₆ alkyl and R¹⁰ representshydrogen, C₁ -C₆ alkyl, benzyl, phenylcarbonyl or C₁ -C₆ alkylcarbonyl.